Esters for use as a base stock and in lubricant applications

ABSTRACT

This invention relates to base ester compounds and complex ester compounds that can be used as a base stock for lubricant applications or a base stock blend component for use in a finished lubricant or for particular applications, and methods of making the same. The base ester compounds and complex esters described herein comprise dimer and/or trimer esters, and their respective branched derivatives.

CROSS REFERENCE TO RELATED APPLICATIONS

A claim of priority for this divisional application under 35 U.S.C. §119is hereby made to the following U.S. nonprovisional patent application:U.S. Serial No. 13/026,268 filed Feb. 13, 2011; and this application isincorporated herein by reference in its entirety.

FIELD OF THE INVENTION

This application relates to base ester compounds and complex estercompounds that can be used as a base stock or a base stock blendcomponent for use in lubricant applications, and methods of making thesame.

BACKGROUND OF THE INVENTION

Lubricants are widely used to reduce friction between surfaces of movingparts and thereby reduce wear and prevent damage to such surfaces andparts. Lubricants are composed primarily of a base stock and one or morelubricant additives. The base stock is generally a relatively highmolecular weight hydrocarbon. In applications where there is a largeamount of pressure applied to moving parts, lubricating compositionscomposed only of hydrocarbon base stock tend to fail and the partsbecome damaged. To make lubricants, such as motor oils, transmissionfluids, gear oils, industrial lubricating oils, metal working oils,etc., one starts with a lubricant grade of petroleum oil from arefinery, or a suitable polymerized petrochemical fluid. Into this basestock, small amounts of additive chemicals are blended therein toimprove material properties and performance, such as enhancinglubricity, inhibiting wear and corrosion of metals, and retarding damageto the fluid from heat and oxidation. As such, various additives such asoxidation and corrosion inhibitors, dispersing agents, high pressureadditives, anti-foaming agents, metal deactivators and other additivessuitable for use in lubricant formulations, can be added in conventionaleffective quantities. It has long been known that synthetic esters canbe used both as a base stock and as an additive in lubricants. Bycomparison with the less expensive, but environmentally less safemineral oils, synthetic esters were mostly used as base oils in caseswhere the viscosity/temperature behavior was expected to meet stringentdemands. The increasingly important issues of environmental acceptanceand biodegradability are the drivers behind the desire for alternativesto mineral oil as a base stock in lubricating applications. Syntheticesters may be polyol esters, polyalphaolefins (PAO), and triglyceridesfound in natural oils. Of key importance to natural oil derivedlubricants are physical properties, such as improved low temperatureproperties, improved viscosity at the full range of operatingconditions, improved oxidative stability (meaning removal of doublebonds in the case of natural oil derived materials), and improvedthermal stability.

Various prior art efforts have attempted to describe esters for use inbiolubricant applications, examples of which include U.S. PatentApplication No. 2009/0198075 titled Synthesis of Diester BasedBiolubricants from Epoxides (“Ref. 1”); Synthesis and PhysicalProperties of Potential Biolubricants Based on Ricinoleic Acid, byLinxing Yao et al., Journal of the American Oil Chemists' Society 87,2010:937-945 (“Ref. 2); Melting Points and Viscosities of Fatty AcidEsters that are Potential Targets for Engineered Oilseed, by Linxing Yaoet al., Journal of the American Oil Chemists' Society 85, 2008:77-82(“Ref. 3”); Diesters from Oleic Acid: Synthesis, Low TemperatureProperties and Oxidation Stability, by Bryan R. Moser et al. Journal ofthe American Oil Chemists' Society 84, 2007:675-680 (“Ref. 4”); OleicAcid Diesters: Synthesis, Characterization and Low-TemperatureProperties, by Jumat Salimon et al., European Journal of ScientificResearch 32(2), 2009, 216-229 (“Ref. 5”); U.S. Pat. No. 6,018,063 titledBiodegradable Oleic Estolide Ester Base Stocks and Lubricants (“Ref.6”); and Oleins as a Source of Estolides for Biolubricant Applications,by L. A. Garcia-Zapateiro et. al., Grasas Y Aceites, 61(2), 2010,171-174 (“Ref. 7”) (collectively, the “cited prior art”). However, noneof the cited prior art references describe improved physical propertiesto the broad extent of the present invention.

SUMMARY OF THE INVENTION

In one aspect of the invention, a lubricant base stock composition isdisclosed, comprising a complex ester having the formula (I):

wherein n1=between 0 and 8; wherein n2=between 0 and 8; whereinm1=between 5 and 9; wherein m2=between 5 and 9; wherein W═OH or OCOR;wherein X═OH or OCOR; wherein Y═OCOR or OH; wherein Z═OH or OCOR; and ingroups W, X, Y, and Z, R=CiHj, wherein i is 2 or greater and j is 5 orgreater.

In another aspect of the invention, a lubricant base stock compositionis disclosed comprising a complex ester having the formula (II):

wherein n1=between 0 and 8; wherein n2=between 0 and 8; whereinm1=between 5 and 9; wherein m2=between 5 and 9; wherein k1=k2=5 orgreater; wherein P═OH or OCOR; wherein Q=OH or OCOR; wherein S═OCOR orOH; wherein T=OH or OCOR; wherein U═OH or OCOR; wherein V═OH or OCOR,and in groups P, Q, S, T, U, and V, R=CiHj, wherein i is 2 or greaterand j is 5 or greater.

In another aspect of the invention, a process for preparing a complexester is disclosed, comprising the steps of: (a) reacting a fattycarboxylic acid having from between about 3 to 36 carbon atoms and afatty alcohol having between about 8 to about 24 carbon atoms, in thepresence of a base, a condensing agent, and a solvent, at temperaturebetween about 4 and 50° C. for about 4 to 36 hours, to produce a baseester; (b) epoxidizing the base ester with a peroxyacid and a solvent attemperature between about 4 and 50° C. for about 4 to 36 hours toproduce an epoxide; (c) reacting the epoxide with another fattycarboxylic acid having from between about 3 to 36 carbon atoms, attemperatures between about 50 and 150° C. for about 4 to 36 hours in anitrogenous atmosphere, to produce said complex ester.

In another aspect of the invention, a process for preparing a complexester comprising the steps of: (a) reacting a fatty carboxylic acidhaving from between about 3 to 36 carbon atoms and a metathesiscatalyst, at temperature between about 30 and 70° C. for about 4 to 36hours, then purified via a solvent to produce a diacid product; (b)reacting said diacid product with fatty alcohol having between about 8to about 24 carbon atoms, in the presence of a base, a condensing agent,and a solvent, at a temperature between about 4 and 50° C. for about 4to 36 hours, to produce a base ester; (b) epoxidizing the base esterwith a peroxyacid and a solvent at temperature between about 4 and 50°C. for about 4 to 36 hours to produce an epoxide; (c) reacting theepoxide with another fatty carboxylic acid having from between about 3to 36 carbon atoms, at temperatures between about 50 and 150° C. forabout 4 to 36 hours in a nitrogenous atmosphere, to produce said complexester.

In another aspect of the invention, a lubricant base stock compositionis disclosed comprising a base ester having the formula (III):

wherein n1=between 0 and 8; wherein n2=between 0 and 8; whereinm1=between 5 and 9; and wherein m2=between 5 and 9.

In another aspect of the invention, a lubricant base stock compositionis disclosed comprising a base ester having the formula (IV):

wherein n1=between 0 and 8; wherein n2=between 0 and 8; whereinm1=between 5 and 9; wherein m2=between 5 and 9; and wherein k1=k2=5.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the synthesis of dimer esters of the present invention.

FIG. 2 depicts a scheme for epoxidation of alkene of the presentinvention.

FIG. 3 depicts a scheme for the ring opening esterification of epoxidesof the present invention.

FIG. 4 depicts the synthesis of dimer ester branched compounds of thepresent invention.

FIG. 4A depicts a generalized structure for the base dimer ester of thepresent invention.

FIG. 4B depicts a generalized structure for the dimer ester branchedderivatives of the present invention.

FIG. 5 depicts the base trimer esters and their branched compounds ofthe present invention.

FIG. 5A depicts a generalized structure for the base trimer esters ofthe present invention.

FIG. 5B depicts a generalized structure for the trimer ester branchedderivatives of the present invention.

FIG. 6 depicts the synthesis of Compound A and its branched derivativesof the present invention.

FIG. 7 depicts the synthesis of Compound B and its branched derivativesof the present invention.

FIG. 8 depicts the synthesis of Compound C and its branched derivativesof the present invention.

FIG. 9 depicts the synthesis of Compound D and its branched derivativesof the present invention.

FIG. 10 depicts the synthesis of Compound E and its branched derivativesof the present invention.

FIG. 11 depicts the synthesis of Compound F and its branched derivativesof the present invention.

FIG. 12 depicts the synthesis of Compound G and its branched derivativesof the present invention.

FIG. 13 depicts the synthesis of (E)-didec-9-enyl octadec-9-enedioate(Compound H) of the present invention.

FIG. 14 depicts the synthesis of Compound H branched derivatives of thepresent invention.

FIG. 15 depicts a general synthesis of branched esters of the presentinvention.

FIG. 16 depicts the ring-opening reaction of the epoxide of Compound Gof the present invention.

FIG. 17 depicts the ring-opening reaction of the epoxide of Compound Eof the present invention.

FIG. 18 depicts the ring-opening reaction of the epoxide of Compound Hof the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present application relates to the compositions and methods forsynthesis of base ester compounds and complex ester compounds for use asa base stock for lubricant applications, or a base stock blend componentfor use in a finished lubricant composition, or for particularapplications. As used herein, base ester compounds may refer to dimeresters and/or trimer esters, where esters shall be understood to includemono-, di-, tri-, tetra-, and higher esters, as applicable. As usedherein, complex esters refers to the respective branched derivatives ofdimer esters, and/or the respective branched derivatives of trimeresters or diesters, or combinations of the respective branchedderivatives of dimer esters and/or the respective branched derivativesof trimer esters and/or their respective branched derivatives. As usedherein, the dimer esters, trimer esters or diesters, and the respectivebranched derivatives of either of these may at times be referred togenerally as compounds, derivatives and/or samples.

The base esters and complex esters in accordance with the presentinvention may constitute a lubricant base stock composition, or a basestock blend component for use in a finished lubricant composition, orthey may be mixed with one or more additives for further optimization asa finished lubricant or for a particular application. Suitableapplications which may be utilized include, but are not limited to,two-cycle engine oils, hydraulic fluids, drilling fluids, greases,compressor oils, cutting fluids, milling fluids, and as emulsifiers formetalworking fluids. Suitable non-limiting examples of additives mayinclude detergents, antiwear agents, antioxidants, metal deactivators,extreme pressure (EP) additives, dispersants, viscosity index improvers,pour point depressants, corrosion protectors, friction coefficientmodifiers, colorants, antifoam agents, demulsifiers and the like. Thebase esters and complex esters in accordance with the present inventionmay also have alternative chemical uses and applications, as understoodby a person skilled in the art. The content of the base esters andcomplex esters of the present invention will typically be present fromabout 0.1 to about 100% by weight, preferably about 25 to about 100% byweight, and most preferably from about 50 to about 100% by weight of afinished lubricant composition.

The dimer esters were prepared at room temperature (typically between17-27° C.) by reacting a fatty carboxylic acid (or its acid halide,preferably an acid chloride created by reacting a fatty carboxylic acidwith a chlorinating agent, such as thionyl chloride, phosphorustrichloride, oxalylchloride or phosphorus pentachloride) and a fattyalcohol with a condensing agent and a catalyst. The trimer esters, andin some embodiments, trimer diesters, were prepared, at roomtemperatures, by reacting an aliphatic dicarboxylic acid, preferably adiacid (or its acid halide, preferably an acid chloride created byreacting an aliphatic dicarboxylic acid with a chlorinating agent, suchas thionyl chloride, phosphorus trichloride, or phosphoruspentachloride) with a fatty alcohol with a condensing agent and acatalyst. Also in some embodiments, the dimer and trimer esters may beprepared via a metathesis route.

The condensing agent typically is a carbodiimide, generally representedby the formula: R¹N═C═NR² wherein R¹ and R² are alkyl groups containingfrom 1 to about 18 carbon atoms, cycloalkyl groups containing 5 to about10 carbon atoms and aryl groups, which term includes alkaryl andarylalkyl groups, containing 5 to about 18 carbon atoms. Non-limitingexamples of such carbodiimides are dimethyl carbodiimide, diisopropylcarbodiimide, diisobutyl carbodiimide, dioctyl carbodiimide, tert-butylisopropyl carbodiimide, dodecyl isopropyl carbodiimide, dicylohexylcarbodiimide, diphenyl carbodiimide, di-o-tolyl carbodiimide,bis(2,6-diethylphenyl) carbodiimide, bis(2,6-diisopropylphenylcarbodiimide, di-beta-naphthyl carbodiimide, benzyl isoopropylcarbodiimide, phenyl-o-tolyl carbodiimide and preferably,dicyclohexylcarbodiimide (DCC).

The catalyst may comprise a base, with non-limiting examples such as atriethyl amine, tripropyl amine, tributyl amine, pyridine and4-dimethylamino pyridine or other pyridine derivative, and preferably,4-dimethylaminopyridine (DMAP).

The solvent used in the esterification and/or epoxidation of the presentinvention may be chosen from the group including but not limited toaliphatic hydrocarbons (e.g., hexane and cyclohexane), organic esters(i.e. ethyl acetate), aromatic hydrocarbons (e.g., benzene and toluene),ethers (e.g., dioxane, tetrahydrofuran, ethyl ether, tert-butyl methylether), halogenated hydrocarbons (e.g., methylene chloride andchloroform), and preferably, chloroform.

The fatty carboxylic acid is derived from a natural oil, withnon-limiting examples such as canola oil, rapeseed oil, coconut oil,corn oil, cottonseed oil, olive oil, palm oil, peanut oil, safflowerseed oil, sesame seed oil, soybean oil, sunflower oil, linseed oil, palmkernel oil, tung oil, jojoba oil, jatropha oil, mustard oil, camellinaoil, pennycress oil, hemp oil, algal oil, castor oil, lard, tallow,poultry fat, yellow grease, fish oil, tall oils, and mixtures thereof.Optionally, the natural oil may be partially and/or fully hydrogenated,and may also be refined, bleached, and/or deodorized. Suitable fattycarboxylic acids of natural oils include, but are not limited to,aliphatic, saturated, unsaturated, straight chain or branched fattyacids having 3 to 36 carbon atoms, such as propionic acid, caproic acid,caprylic acid, capric acid, caproleic acid (9-decenoic acid), lauricacid, nonanoic acid, myristic acid, palmitic acid, oleic acid, linoleicacid, linolenic acid, stearic acid, arachic acid, erucic acid andbehenic acid.

The alcohol is typically a fatty alcohol of between 8 and 24 carbonatoms. The fatty alcohols are meant herein to include monohydric andpolyhydric fatty alcohols, particularly those containing 8 to 24 carbonatoms exhibiting straight-chain or branched-chain structure, which aresaturated or unsaturated (containing one or more carbon-carbon doublebonds). Non-limiting examples of fatty alcohols include oleic,linolenic, linolenic, lauric, caproic, erucic, myristic and palmiticalcohols, as well as mixtures of any of the foregoing fatty alcohols. Insome embodiments, the fatty alcohol may be an unsaturated primaryalcohol such as 9-decen-1-ol, which is derived from 9-decenoic acid.

Following the above esterification, the base esters were epoxidized viaany suitable peroxyacid. Peroxyacids (peracids) are acyl hydroperoxidesand are most commonly produced by the acid-catalyzed esterification ofhydrogen peroxide. Any peroxyacid may be used in the epoxidationreaction. The peroxyacids may be formed in-situ by reacting ahydroperoxide with the corresponding acid, such as formic or aceticacid. Examples of hydroperoxides that may be used include, but are notlimited to, hydrogen peroxide, tert-butylhydroperoxide,triphenylsilylhydroperoxide, cumylhydroperoxide, and preferably,hydrogen peroxide. Other commercial organic peracids may also be used,such as benzoyl peroxide, and potassium persulfate. Commonly usedsolvents in the epoxidation of the present invention may be chosen fromthe group including but not limited to aliphatic hydrocarbons (e.g.,hexane and cyclohexane), organic esters (i.e. ethyl acetate), aromatichydrocarbons (e.g., benzene and toluene), ethers (e.g., dioxane,tetrahydrofuran, ethyl ether, tert-butyl methyl ether), halogenatedhydrocarbons (e.g., methylene chloride and chloroform), and preferably,methylene chloride.

Following epoxidation, the addition of any suitable fatty carboxylicacids, typically having between 3 and 36 carbon atoms, preferably,propionic or nonanoic acid, was utilized to produce branched compounds,with further details as described later in this document.

In certain embodiments (compounds E, F, G, and H, and their branchedderivatives), the fatty carboxylic acid derived from the natural oil maybe metathesized in the presence of a metathesis catalyst. Metathesis isa catalytic reaction that involves the interchange of alkylidene unitsamong compounds containing one or more double bonds (i.e., olefiniccompounds) via the formation and cleavage of the carbon-carbon doublebonds.

The metathesis catalyst in this reaction may include any catalyst orcatalyst system that catalyzes a metathesis reaction. Any knownmetathesis catalyst may be used, alone or in combination with one ormore additional catalysts. Non-limiting exemplary metathesis catalystsand process conditions are described in PCT/US2008/009635, pp. 18-47,incorporated by reference herein. A number of the metathesis catalystsas shown are manufactured by Materia, Inc. (Pasadena, Calif.).

With regards to compounds E, F, G, and H, and their branchedderivatives, 9-decenoic acid may be formed by the cross-metathesis ofoleic acid or methyl oleate, found in or derived from natural oils, withethene, propene, butene, hexene, and/or a higher alpha-olefin whichproduces 9-decenoic acid (or the corresponding ester of decenoic acid ifan ester (e.g., the methyl ester) of oleic acid is employed), and1-decene. The cross-metathesis of oleic acid or methyl oleate withethene, propene, butene and/or a higher alpha-olefin is carried out inthe presence of a metathesis catalyst under suitable metathesis reactionconditions. Also, in some embodiments, compounds E, F, G and H may beprepared by cross-metathesis from compound A and an olefin having aterminal carbon double bond (such as those described in the precedingsentence). Generally, cross metathesis may be represented schematicallyas shown in Equation I:

R¹—CH═CH—R²+R³—CH═CH—R⁴

R¹—CH═CH—R³+R¹—CH═CH—R⁴+R²—CH═CH—R³+R²—CH═CH—R⁴+R¹—CH═CH—R¹+R²—CH═CH—R²+R³—CH═CH—R³+R⁴—CH═CH—R⁴  (I)

-   -   wherein R¹, R², R³, and R⁴ are organic groups.

In some embodiments, compound H may be prepared by self-metathesis viacompound G (metathesis occurring between two of the same molecules, inthis case, compound G). Generally, self-metathesis may be representedschematically as shown in Equation II below.

R¹—CH═CH—R²+R¹—CH═CH—R²

R¹—CH═CH—R¹+R²—CH═CH—R²  (II)

-   -   wherein R¹ and R² are organic groups.

In some embodiments, the 9-decenoic acid may be reduced to 9-decen-1-olusing a typical reducing agent under conditions known to a personskilled in the art. The reducing agent is typically a hydride reagentsuch as lithium aluminum hydride and boron hydrides such as sodiumborohydride, diborane, and 9-borabicyclo[3.3.1]nonane (9-BBN);preferably, the reducing agent is lithium aluminum hydride. In thealternative, an ester of the 9-decenoic acid, such as methyl9-decenoate, may be hydrogenated into 9-decen-1-ol with a hydrogencontaining gas and in the presence of a catalyst system, underhydrogenation conditions known to a person skilled in the art. The9-decen-1-ol may be reacted with a suitable fatty carboxylic acid or itsacid chloride as stated below for specific compounds.

A non-limiting listing of representative dimer esters produced by theprocess of this invention is listed below in Table 1.

TABLE 1 Dimer Esters and their branched derivatives synthesized (thecolumn headed “Structure” refers to the structures shown in FIGS. 1, 4,and 4A). Compounds Name Structure A Octadec-9-enoic acid octadec-9-enylester n1 = n2 = 8 m1 = m2 = 5 B Docos-13-enoic acid octadec-9-enyl estern1 = n2 = 8 m1 = 9; m2 = 5 C Docos-13-enoic acid docos-13-enyl ester n1= n2 = 8 m1 = m2 = 9 D Octadec-9-enoic acid docos-13-enyl ester n1 = n2= 8 m1 = 5; m2 = 9 E octadec-9-enyl dec-9-enoate n1 = 0; n2 = 8 m1 = m2= 5 F dec-9-enyl oleate n1 = 8; n2 = 0 m1 = m2 = 5 G dec-9-enyldec-9-enoate n1 = n2 = 0 m1 = m2 = 5 A29(10)-hydroxy-10(9)-(propionyloxy)octadecyl n1 = n2 = 89(10)-hydroxy-10(9)- m1 = m2 = 5 (propionyloxy)octadecanoate R = C₂H₅A2-II 9(10)-hydroxy-10(9)-(nonanoyloxy)octadecyl n1 = n2 = 89(10)-hydroxy-10(9)- m1 = m2 = 5 (nonanoyloxy)octadecanoate R = C₈H₁₇ A31-(9(10)-hydroxy-10(9)- n1 = n2 = 8(propionyloxy)octadecanoyloxy)octadecane- m1 = m2 = 59,10-diyldipropionate or/and 1-(9(10)-hydroxy- R = C₂H₅10(9)-(propionyloxy)octadecyloxy)-1- oxooctadecane-9,10-diyldipropionate A4 1-(9,10- n1 = n2 = 8bis(propionyloxy)octadecanoyloxy)octadecane- m1 = m2 = 5 9,10-diyldipropionate R = C₂H₅ B2 10(9)-hydroxy-9(10)-(propionyloxy)octadecyl n1= n2 = 8 13(14)-hydroxy-14(13)- m1 = 9; m2 = 5 (propionyloxy)docosanoateR = C₂H₅ B3 22-(10(9)-hydroxy-9(10)- n1 = n2 = 8(propionyloxy)octadecyloxy)-22-oxodocosane- m1 = 9; m2 = 5 9,10-diyldipropionate or/and 1-(13(14)-hydroxy- R = C₂H₅ 14(13)-(propionyloxy)docosanoyloxy)octadecane-9,10- diyl dipropionate B41-(13,14- n1 = n2 = 8 bis(propionyloxy)docosanoyloxy)octadecane- m1 = 9;m2 = 5 9,10-diyl dipropionate R = C₂H₅ C213(14)-hydroxy-14(13)-(propionyloxy)docosyl n1 = n2 = 813(14)-hydroxy-14(13)- m1 = m2 = 9 (propionyloxy)docosanoate R = C₂H₅C2-II 13(14)-hydroxy-14(13)-(nonanoyloxy)docosyl n1 = n2 = 813(14)-hydroxy-14(13)- m1 = m2 = 9 (nonanoyloxy)docosanoate R = C₈H₁₇ C322-(13(14)-hydroxy-14(13)- n1 = n2 = 8(propionyloxy)docosyloxy)-22-oxodocosane- m1 = m2 = 9 9,10-diyldipropionate or/and 22-(13(14)-hydroxy- R = C₂H₅14(13)-(propionyloxy)docosanoyloxy)docosane- 9,10-diyl dipropionate C422-(13,14- n1 = n2 = 8 bis(propionyloxy)docosanoyloxy)docosane- m1 = m2= 9 9,10-diyl dipropionate R = C₂H₅ D214(13)-hydroxy-13(14)-(propionyloxy)docosyl n1 = n2 = 89(10)-hydroxy-10(9)- m1 = 5; m2 = 9 (propionyloxy)octadecanoate R = C₂H₅D3 22-(9(10)-hydroxy-10(9)- n1 = n2 = 8(propionyloxy)octadecanoyloxy)docosane-9,10- m1 = 5; m2 = 9 diyldipropionate or/and 1-(14(13)-hydroxy- R = C₂H₅13(14)-(propionyloxy)docosyloxy)-1- oxooctadecane-9,10-diyl dipropionateD4 1-(13,14-bis(propionyloxy)docosyloxy)-1- n1 = n2 = 8oxooctadecane-9,10-diyl dipropionate m1 = 5; m2 = 9 R = C₂H₅ E2-110(9)-hydroxy-9(10)-(propionyloxy)octadecyl 9- n1 = 0; n2 = 8hydroxy-10-(propionyloxy)decanoate m1 = m2 = 5 R = C₂H₅ E2-210(9)-hydroxy-9(10)-(propionyloxy)octadecyl 10- n1 = 0; n2 = 8hydroxy-9-(propionyloxy)decanoate m1 = m2 = 5 R = C₂H₅ E310-(10(9)-hydroxy-9(10)- n1 = 0; n2 = 8(propionyloxy)octadecyloxy)-10-oxodecane-1,2- m1 = m2 = 5 diyldipropionate R = C₂H₅ E4 1-(9,10- n1 = 0; n2 = 8bis(propionyloxy)decanoyloxy)octadecane-9,10- m1 = m2 = 5 diyldipropionate R = C₂H₅ F2-1 9-hydroxy-10-(propionyloxy)decyl9(10)-hydroxy- n1 = 8; n2 = 0 10(9)-(propionyloxy)octadecanoate m1 = m2= 5 R = C₂H₅ F2-2 10-hydroxy-9-(propionyloxy)decyl 9(10)-hydroxy- n1 =8; n2 = 0 10(9)-(propionyloxy)octadecanoate m1 = m2 = 5 R = C₂H₅ F310-(9(10)-hydroxy-10(9)- n1 = 8; n2 = 0(propionyloxy)octadecanoyloxy)decane-1,2-diyl m1 = m2 = 5 dipropionate R= C₂H₅ F4 1-(9,10-bis(propionyloxy)decyloxy)-1- n1 = 8; n2 = 0oxooctadecane-9,10-diyl dipropionate m1 = m2 = 5 R = C₂H₅ G2-19-hydroxy-10-(propionyloxy)decyl 9-hydroxy-10- n1 = n2 = 0(propionyloxy)decanoate m1 = m2 = 5 R = C₂H₅ G2-210-hydroxy-9-(propionyloxy)decyl 9-hydroxy-10- n1 = n2 = 0(propionyloxy)decanoate or/and 9-hydroxy-10- m1 = m2 = 5(propionyloxy)decyl 10-hydroxy-9- R = C₂H₅ (propionyloxy)decanoate G3-110-(9-hydroxy-10- n1 = n2 = 0 (propionyloxy)decanoyloxy)decane-1,2-diylm1 = m2 = 5 dipropionate or/and 10-(9-hydroxy-10- R = C₂H₅(propionyloxy)decyloxy)-10-oxodecane-1,2-diyl dipropionate G3-210-(10-hydroxy-9- n1 = n2 = 0 (propionyloxy)decanoyloxy)decane-1,2-diylm1 = m2 = 5 dipropionate or/and 10-(10-hydroxy-9- R = C₂H₅(propionyloxy)decyloxy)-10-oxodecane-1,2-diyl dipropionate G410-(9,10-bis(propionyloxy)decanoyloxy)decane- n1 = n2 = 0 1,2-diyldipropionate m1 = m2 = 5 R = C₂H₅

TABLE 2 Trimer Esters and their branched derivatives synthesized (thecolumn headed “Structure” refers to the structures shown in FIGS. 5 and5A). Com- pounds Name Structure H E-didec-9-enyl octadec-9-enedioate n1= n2 = 0; m1 = m2 = 5; k1 = k2 = 5 H3 1-(9(10)-hydroxy-10(9)- n1 = n2 =0; (propionyloxy)decyl) 18-(10(9)- m1 = m2 = 5;hydroxy-9(10)-(propionyloxy)decyl)-9(10)- k1 = k2 = 5hydroxy-10(9)-(propionyloxy)octadecanedioate R = C₂H₅ H41-(9,10-bis(propionyloxy)decyl) 18-(9(10)- n1 = n2 = 0;hydroxy-10(9)-(propionyloxy)decyl) 10(9)- m1 = m2 = 5;hydroxy-9(10)-(propionyloxy)octadecanedioate k1 = k2 = 5 R = C₂H₅ H5 Bis(9,10-bis(propionyloxy)decyl)9(10)- n1 = n2 = 0;hydroxy-10(9)-(propionyloxy)octadecandioate m1 = m2 = 5; k1 = k2 = 5 R =C₂H₅ H6 Bis (9,10-bis(propionyloxy)decyl)9,10-bis n1 = n2 = 0;(propionyloxy)octadecanedioate m1 = m2 = 5; k1 = k2 = 5 R = C₂H₅

The dimer esters presented were prepared by two general proceduresdescribed in FIG. 1, with specifics described for each compound A-Gdescribed later below:

Procedure 1:

To a solution of fatty alcohol (typically 1-100 mmol, preferably 5-50mmol, and most preferably, 10 mmol) in Chloroform (typically 1-100 mL,preferably 10-50 mL, and most preferably, 20 mL), fatty acid (typically1-100 mmol, preferably 5-50 mmol, and most preferably 10.1 mmol),4-dimethylaminopyridine (typically 1-100 mmol, preferably 5-50 mmol, andmost preferably 10 mmol) was added. To this reaction mixture in an icebath, dicyclohexyl-carbodiimide (typically 1-100 mmol, preferably 5-50mmol, and most preferably 11 mmol) in Chloroform was added slowly andthe reaction was stirred at a temperature (typically between 4-50° C.,preferably between 12-33° C., and most preferably between 17-27° C.)overnight. The precipitated dicyclohexylurea was removed by filtration.The organic phase was then washed sequentially with water, 5% HCl, 4%NaHCO3, water. The solvents were roto-evaporated and the residue waspurified by column chromatography with Ethyl Acetate/Hexane to give acolorless oil.

Procedure 2:

To a solution of fatty alcohol (typically 1-100 mmol, preferably 5-50mmol, and most preferably 10 mmol) in chloroform (typically 1-100 mL,preferably 10-50 mL, and most preferably 30 mL), acyl chloride(typically 1-100 mmol, preferably 5-50 mmol, and most preferably 10mmol) was added. Pyridine (typically 1-100 mmol, preferably 5-50 mmol,and most preferably 12 mmol) was then added to the reaction solutiondrop wise. The reaction mixture was stirred at a temperature (typicallybetween 4-50° C., preferably between 12-33° C., and most preferablybetween 17-27° C.) overnight. The reaction mixture was then diluted withanother amount of Chloroform (typically 1-300 mL, preferably 100-200 mL,and most preferably 160 mL). The organic layer was washed with water(3×50 mL), followed by 5% HCl (2×50 mL), water (2×50 mL), 4% NaHCO₃(2×50 mL) and water (3×50 mL).

The organic layer was dried over Na₂SO₄. After chloroform was removed,the residue was purified by column chromatography with Ethylacetate/Hexane to give a colorless oil.

The synthesis of the esters were followed by epoxidation with peroxyacidwhich was formed from formic acid and hydrogen peroxide in situ to giveepoxides (FIG. 2) with CH₂Cl₂ (methylene chloride) used as solvent.Compared to the reaction without CH₂Cl₂, epoxidation with CH₂Cl₂ as asolvent was faster with fewer side-products, since CH₂Cl₂ improves thesolubility of the reagents in the reaction. Epoxidations of compounds E,F and G, with terminal double bonds, were slower (˜36 hours as opposedto ˜5 hours for the epoxidations of compounds A, B, C and D) because thealkyl group on the carbon double bond in compounds A, B and C canincrease the rate of epoxidation.

To a stirred solution of ester (typically 1-100 mmol, preferably 5-50mmol, and most preferably 10 mmol) and formic acid (typically 1-100mmol, preferably 20-80 mmol, and most preferably 60 mmol) in CH₂Cl₂(typically 1-100 mL, preferably 5-50 mL, and most preferably 10 mL) at4° C., H₂O₂ (typically 1-100 mmol, preferably 5-70 mmol, and mostpreferably 44 mmol) was slowly added. The reaction proceeded at atemperature (typically between 4-50° C., preferably between 12-33° C.,and most preferably between 17-27° C.) with vigorous stirring for 4-36hrs. After removal of the aqueous phase, additional CH₂Cl₂ (30 mL) wasadded to the organic phase, which was washed sequentially with water(2×20 mL), saturated aqueous NaHCO₃ (2×10 mL) and brine (2×20 mL), thendried on Na₂SO₄, filtered, and concentrated. The residue was purified bycolumn chromatography with Ethyl acetate/Hexane to give white crystals.

I. Synthesis of Dimer and Trimer Esters and Branched Derivatives ofDimer and Trimer Esters

The addition of carboxylic acids to the epoxides by ring-openingesterification was accomplished to give branched compounds without needfor either a further catalyst or further solvent as shown in FIGS. 2 and3. The reactions with 2-branched compounds as main products were carriedout at typically between 50-150° C., preferably between about 70-120°C., and most preferably at about 95° C., but those with 3- and4-branched compounds were carried out at typically between 60-160° C.,preferably between about 80-140° C., and most preferably at about 120°C., where water produced in the reactions was partially removed.

For branched compounds derived from compounds A, B, C and D, no effortto distinguish the regiochemistry(9-alkanonate-10-hydroxy-oactadecanoate versus the equally likely alkyl10-alkanoate-9-9hydroxyoctadecanoate regio-isomer) or thestereochemistry (S, or R at C9 and C10) of the polyol esters was madedue to the laborious chromatography required and the economics involvedat potentially larger commercial scales. However, for those branchedcompounds derived from compounds E, F and G, in consideration of thefact that the position of hydroxyl group or carboxyl acid branch at thechain end would have significant influence on their properties, andsince the differences in their polarity makes them easier to separate,the regio-isomers (but not stereo-isomers) were separated.

To the epoxidation products above, (typically 1-100 mmol, preferably5-50 mmol, and most preferably 10 mmol), propionic acid or nonanoic acid(typically 1-400 mmol, preferably 100-300 mmol, and most preferably 220mmol) was added. The reaction was carried out under an N₂ atmosphere andheated to typically between 50-150° C., preferably between about 70-120°C., and most preferably at 95° C. and stirred at 95° C. for typicallybetween about 4 to 36 hours, preferably 10-20 hours, and most preferably16 hours. To achieve 3 or 4 branches in the compounds, the reactiontemperature was raised to typically between 60-160° C., preferablybetween about 80-140° C., and most preferably at 120° C. The resultingproducts were poured into 200 mL of water and extracted with Ethylacetate (2×50 mL). The organic phase was washed sequentially by water(2×100 mL), saturated aqueousNaHCO₃ (2×100 mL) and brine (2×200 mL),dried on Na₂SO₄, and concentrated. The residue was purified by columnchromatography with Ethyl Acetate/Hexane.

The dimer ester branched derivatives were prepared by the synthesisshown in FIG. 4. The respective dimer esters are depicted by thegeneralized structure in FIG. 4A, wherein n1=between 0 and 8; whereinn2=between 0 and 8; wherein m1=between 5 and 9; and wherein m2=between 5and 9.

In a generalized manner, the syntheses of the dimer ester branchedcompounds yields a compound as depicted in FIG. 4B, wherein n1 isbetween 0 and 8; wherein n2 is between 0 and 8; wherein m1 is between 5and 9; wherein m2 is between 5 and 9; wherein W is OH or OCOR; wherein Xis OH or OCOR; wherein Y is OCOR or OH; wherein Z is OH or OCOR; and ingroups W, X, Y, and Z, R=CiHj, wherein i is 2 or greater and j is 5 orgreater.

The trimer esters presented (Compound H) and its branched derivativesare depicted as shown in FIG. 5. The respective base trimer ester isdepicted by the generalized structure in FIG. 5A, wherein n1=between 0and 8; wherein n2=between 0 and 8; wherein m1=between 5 and 9; whereinm2=between 5 and 9; and wherein k1=k2=5.

In a generalized manner, the syntheses of the trimer ester branchedcompounds yields a compound as depicted in FIG. 5B, wherein n1 isbetween 0 and 8; wherein n2 is between 0 and 8; wherein m1 is between 5and 9; wherein m2 is between 5 and 9; wherein k1=k2=5 or greater;wherein P═OH or OCOR; wherein Q=OH or OCOR; wherein S═OCOR or OH;wherein T=OH or OCOR; wherein U═OH or OCOR; wherein V═OH or OCOR, and ingroups P, Q, S, T, U, and V, R═CiHj, wherein i is 2 or greater and j is5 or greater.

The compounds presented in Table 1 and Table 2 above were characterizedwith a combination of nuclear magnetic resonance (1H-NMR), highperformance liquid chromatography (HPLC), and/or mass spectrometry (MS),as shown in Table 3 below.

TABLE 3 Characterization of Compounds Characterization methods Compounds1H-NMR HPLC-Fid MS A Yes No No B Yes No No C Yes No No D Yes No No E YesNo No F Yes No No G Yes No No A2 Yes No No A2-II Yes No No A3 Yes No NoA4 Yes No No B2 Yes No No B3 Yes No No B4 Yes No No C2 Yes No No C2-IIYes No No C3 Yes No No C4 Yes No No D2 Yes Yes No D3 Yes No No D4 YesYes No E2-1 Yes Yes Yes E2-2 Yes Yes No E3 Yes Yes No E4 Yes Yes No F2-1Yes Yes No F2-2 Yes Yes No F3 Yes Yes Yes F4 Yes Yes Yes G2-1 Yes Yes NoG2-2 Yes No Yes G3-1 Yes Yes Yes G3-2 Yes No No G4 Yes Yes No H Yes NoNo H3 Yes Yes Yes H4 Yes Yes Yes H5 Yes Yes Yes H6 Yes Yes Yes

The synthesis of the individual dimer and trimer esters, their epoxides,and their branched derivatives, are provided below:

Octadec-9-enoic acid octadec-9-enyl ester (Compound A)

Compound A was prepared from Oleoyl chloride and Oleyl alcohol in thepresence of pyridine following the general procedure discussed beforeand as shown in FIG. 6. Pure compound A was a colorless oil obtained bycolumn chromatography with Ethyl acetate/Hexane=1:30. Reactionconditions for branched derivative compounds A2, A3, and A4 are alsoshown below.

Yield: 98.5%

1H-NMR in CDCl₃ (ppm): 5.4 (4, m), 4.1 (2, t), 2.3 (2, t), 2.1-2.0 (8,m), 1.7-1.56 (4, m), 1.44-1.20 (42, m), 0.86-0.76 (6, t)

Purity: >95%

Docos-13-enoic acid octadec-9-enyl ester (Compound B)

Compound B was prepared from Erucic acid and Oleyl alcohol in thepresence of DCC and DMAP following the general procedure discussedbefore and as shown in FIG. 7. Pure compound B was a colorless oilobtained by column chromatography with Ethyl acetate/Hexane=1:40.Reaction conditions for branched derivative compounds B2, B3, and B4 arealso shown below.

Yield: 91.8%

1H-NMR in CDCl₃ (ppm), 5.4 (4, m), 4.1 (2, t), 2.3 (2, t), 2.1-2.0 (8,m), 1.7-1.56 (4, m), 1.44-1.20 (50, m), 0.86-0.76 (6, t)

Purity: >95%

Docos-13-enoic acid docos-13-enyl ester (Compound C)

Compound C was prepared from Erucic acid and Erucic alcohol withpresence of DCC and DMAP following the general procedure discussedbefore and as shown in FIG. 8. Pure compound C was a colorless oilobtained by column chromatography with Ethyl acetate/Hexane=1:40.Reaction conditions for branched derivative compounds C2, C3, and C4 arealso shown below.

Yield: 95%

1H-NMR in CDCl₃ (ppm), 5.4 (4, m), 4.1 (2, t), 2.3 (2, t), 2.1-2.0 (8,m), 1.7-1.56 (4, m), 1.44-1.20 (58, m), 0.86-0.76 (6, t)

Purity: >95%

Octadec-9-enoic acid docos-13-enyl ester (Compound D)

Compound D was prepared from Oleoyl chloride and Erucic acid followingthe general procedure discussed before and as shown in FIG. 9. Purecompound D was a colorless oil obtained by column chromatography withEthyl acetate/Hexane=1:40. Reaction conditions for branched derivativecompounds D2, D3, and D4 are also shown below.

Yield: 94.5%

1H-NMR in CDCl₃ (ppm), 5.4 (4, m), 4.1 (2, t), 2.3 (2, t), 2.1-2.0 (8,m), 1.7-1.56 (4, m), 1.44-1.20 (50, m), 0.86-0.76 (6, t)

Purity: >95%

Octadec-9-enyl dec-9-enoate (Compound E)

Compound E was prepared from Oleyl alcohol and 9-decenoic acid followingthe general procedure previously discussed and shown in FIG. 10. Purecompound E was a colorless oil obtained by column chromatography withEthyl acetate/Hexane=1:40.

Yield: 96%

1H-NMR in CDCl₃ (ppm), 5.8 (1, m), 5.4 (2, m), 5.0 (2, dd), 4.1 (2, t),2.3 (2, t), 2.0 (6, m), 1.6 (4, m), 1.4-1.2 (30, m), 0.9 (3, t)

Purity: >95%

Dec-9-enyl oleate (Compound F)

Compound F was prepared from Oleoyl chloride and 9-decen-1-ol followingthe general procedure already discussed and shown in FIG. 11. Purecompound F was a colorless oil obtained by column chromatography withEthyl acetate/Hexane=1:40.

Yield: 97.5%

1H-NMR in CDCl₃ (ppm), 5.8 (1, m), 5.4 (2, m), 5.0 (2, dd), 4.1 (2, t),2.3 (2, t), 2.0 (6, m), 1.6 (4, m), 1.4-1.2 (30, m), 0.9 (6, t)

Purity: >95%

Dec-9-enyl dec-9-enoate (Compound G)

Compound G was prepared from 9-decen-1-ol and 9-decenoic acid followingthe general procedure already discussed and shown in FIG. 12. Purecompound G was a colorless oil by column chromatography with Ethylacetate/Hexane=1:50.

Yield: 92.7%

1H-NMR in CDCl₃ (ppm), 5.8 (2, m), 5.0 (4, dd), 4.0 (2, t), 2.3 (2, t),2.0 (4, m), 1.6 (4, m), 1.4-1.2 (18, m)

Purity: >95%

8-(3-octyloxiran-2-yl) octyl 8-(3-octyloxiran-2-yl) octanoate (Epoxidesof A)

Epoxide was prepared from compound A with H₂O₂ and Formic acid as shownin FIG. 6. Pure compound was obtained by column chromatography withEthyl acetate/Hexane=1:30.

Yield: 70%

1H-NMR in CDCl₃ (ppm): 4.1 (2, t), 2.9 (4, Br), 2.3 (2, t), 2.1-2.0 (8,m), 1.7-1.6 (4, m), 1.5-1.20 (42, m), 0.86-0.76 (6, t)

Purity: >95%

8-(3-octyloxiran-2-yl) octyl 12-(3-octyloxiran-2-yl) dodecanoate(Epoxide of B)

Epoxide was prepared from compound B with H₂O₂ and Formic acid withCH₂Cl₂ as a solvent as shown in FIG. 7. Pure compound was obtained bycolumn chromatography with Ethyl acetate/Hexane=1:20.

Yield: 75%

1H-NMR in CDCl₃ (ppm), 4.1 (2, t), 2.9 (4, br), 2.3 (2, t), 2.1-2.0 (8,m), 1.7-1.56 (4, m), 1.44-1.20 (50, m), 0.86-0.76 (6, t)

Purity: >95%

12-(3-octyloxiran-2-yl) dodecyl 12-(3-octyloxiran-2-yl) dodecanoate(Epoxide of C)

Epoxide was prepared from compound C with H₂O₂ and Formic acid and themixture of Hexane (20 mL) and Ethyl acetate (10 mL) as solvent (Shown inFIG. 8). Pure compound was obtained by column chromatography with Ethylacetate/Hexane=1:20 as white solid.

Yield: 73%

1H-NMR in CDCl₃ (ppm), 4.1 (2, t), 2.9 (4, br), 2.3 (2, t), 2.1-2.0 (8,m), 1.7-1.56 (4, m), 1.44-1.20 (58, m), 0.86-0.76 (6, t)

Purity: >95%

12-(3-octyloxiran-2-yl)dodecyl 8-(3-octyloxiran-2-yl)octanoate (Epoxideof D)

Epoxide was prepared from compound D with H₂O₂ and Formic acid withCH₂Cl₂ as solvent (shown in FIG. 9). Pure compounds was obtained bycolumn chromatography with Ethyl acetate/Hexane=1:30 as white solid.

Yield: 72.7%

1H-NMR in CDCl₃ (ppm), 4.1 (2, t), 2.9 (4, br), 2.3 (2, t), 2.1-2.0 (8,m), 1.7-1.56 (4, m), 1.44-1.20 (50, m), 0.86-0.76 (6, t)

Purity: >95%

8-(3-octyloxiran-2-yl)octyl 8-(oxiran-2-yl)octanoate (Epoxide of E)

Epoxide was prepared from compound E with H₂O₂ and Formic acid withCH₂Cl₂ as solvent and at room temperature for 28 hours (shown in FIG.10). Pure compounds was obtained by column chromatography with Ethylacetate/Hexane=1:10 as colorless oil.

Yield: 75.6%

1H-NMR in CDCl₃ (ppm), 4.1 (2, t), 2.9 (3, br), 2.8 (1, t), 2.5 (1, t,)2.3 (2, t), 1.6-1.2 (40, m), 0.9 (3, t)

Purity: >95%

8-(oxiran-2-yl)octyl 8-(3-octyloxiran-2-yl)octanoate (Epoxide of F)

Epoxide was prepared from compound F with H₂O₂ and Formic acid withCH₂Cl₂ as solvent and at room temperature for 48 hours (shown in FIG.11). Pure compounds was obtained by column chromatography with Ethylacetate/Hexane=1:10 as colorless oil.

Yield: 71.4%

1H-NMR in CDCl₃ (ppm), 4.1 (2, t), 2.9 (3, br), 2.8 (1, t), 2.5 (1, t,)2.3 (2, t), 1.6-1.2 (40, m), 0.9 (3, t)

Purity: >95%

8-(oxiran-2-yl)octyl 8-(oxiran-2-yl)octanoate (Epoxide of G)

Epoxide was prepared from compound F with H₂O₂ and Formic acid withCH₂Cl₂ as solvent and at room temperature for 48 hours (shown in FIG.12). Pure compounds was obtained by column chromatography with Ethylacetate/Hexane=1:10 as colorless oil.

Yield: 72%

1H-NMR in CDCl₃ (ppm), 4.0 (2, t), 3.0 (2, br), 2.7 (2, t), 2.5 (2, t),2.3 (2, t), 1.6-1.2 (27, m)

Purity: >95%

Branched Derivatives of Compound A

Branched compound A derivatives were prepared from epoxide of compound Aand propionic acid (or nonanoic acid for A2-II) at 95° C. for A2 and A3or 120° C. for A3 and A4 (Shown in FIG. 6).

9(10)-hydroxy-10(9)-(propionyloxy) octadecyl9(10)-hydroxy-10(9)-(propionyloxy) octadecanoate (A2)

Pure compound A2 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:10.

Yield: 89.5%

1H-NMR in CDCl₃ (ppm), 4.8 (2, m), 4.1 (2, t), 3.7-3.5 (2, m), 2.4-2.2(6, m), 1.5-1.2 (46, m), 1.1 (6, t), 0.8 (6, t)

Purity >95%

9(10)-hydroxy-10(9)-(nonanoyloxy) octadecyl9(10)-hydroxy-10(9)-(nonanoyloxy) octadecanoate (A2-II)

Pure compound A2-II was given as colorless oil by column chromatographywith Ethyl Acetate/Hexane=1:10.

Yield: 64%

1H-NMR in CDCl₃ (ppm), 4.8 (2, m), 4.1 (2, t), 3.7-3.5 (2, m), 2.4-2.2(6, m), 1.6 (16, m), 1.5-1.2 (62, m), 0.8 (12, t)

Purity: >95%

1-(9(10)-hydroxy-10(9)-(propionyloxy) octadecanoyloxy)octadecane-9,10-diyldipropionate or/and1-(9(10)-hydroxy-10(9)-(propionyloxy)octadecyloxy)-1-oxooctadecane-9,10-diyl dipropionate (A3)

Pure compound A3 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:6.

Yield: 30.6% A4+38.2% A3 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.0 (2, m), 4.8 (1, m), 4.0 (2, t), 3.6 (1, m),2.4-2.2 (8, m), 1.8-1.2 (55, m), 1.1 (9, t), 0.8 (6, t)

Purity: >95%

1-(9,10-bis(propionyloxy)octadecanoyloxy)octadecane-9,10-diyldipropionate (A4)

Pure compound A4 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:10.

Yield: 30.6% A4+38.2% A3 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.0 (4, m), 4.0 (2, t), 2.4-2.2 (10, m), 1.7-1.5(6, m), 1.4-1.2 (48, m), 1.1 (12, t), 0.8 (6, t)

Purity: >95%

Branched Derivatives of Compound B

Branched Compound B derivatives were prepared from the epoxide ofcompound B and propionic acid at 95° C. for B2 and B3 or 120° C. for B3and B4 (shown FIG. 7).

10(9)-hydroxy-9(10)-(propionyloxy) octadecyl13(14)-hydroxy-14(13)-(propionyloxy) docosanoate (B2)

Pure compound B2 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:8.

Yield: 47.8% B2+29% B3 at 95° C.; 46% B2+35.7% B3+11.3% B4 at 120° C.

1H-NMR in CDCl₃ (ppm), 4.8 (2, m), 4.0 (2, t), 3.6 (2, br), 2.3 (4, q),2.2 (2, t), 1.8-1.5 (10, m), 1.5-1.2 (56, m), 1.1 (6, t), 0.8 (6, t)

Purity: >95%

22-(10(9)-hydroxy-9(10)-(propionyloxy)octadecyloxy)-22-oxodocosane-9,10-diyldipropionate or/and1-(13(14)-hydroxy-14(13)-(propionyloxy)docosanoyloxy)octadecane-9,10-diyldipropionate (B3)

Pure compound B3 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:10.

Yield: 47.8% B2+29% B3 at 95° C.; 46% B2+35.7% B3+11.3% B4 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.0 (2, m), 4.8 (1, m), 4.0 (2, t), 3.6 (1, br),2.4-2.2 (8, m), 1.7-1.2 (63, m), 1.1 (9, t), 0.8 (6, t)

Purity: >95%

1-(13,14-bis(propionyloxy)docosanoyloxy)octadecane-9,10-diyldipropionate (B4)

Pure compound B4 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:10.

Yield: 46% B2+35.7% B3+11.3% B4 at 120° C.

1H-NMR in CDCl₃ (ppm), 4.8 (4, m), 3.6 (2, t), 2.2-2.0 (10, m), 1.4-1.2(12, br), 1.1-0.9 (50, m), 0.8 (12, t), 0.6 (6, t)

Purity: >95%

Branched Derivatives of Compound C

Branched Compound C derivatives were prepared from epoxide of compound Cand propionic acid (or nonanoic acid for C2-II) at 95° C. for compoundsC2 and C3 or 120° C. for C3 and C4 (shown in FIG. 8).

13(14)-hydroxy-14(13)-(propionyloxy)docosyl13(14)-hydroxy-14(13)-(propionyloxy)docosanoate (C2)

Pure compound C2 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:8.

Yield: 71.6% C2 and 17.9% C3 at 95° C.

1H-NMR in CDCl₃ (ppm), 4.8 (2, m), 4.1 (2, t), 3.6 (2, br), 2.4 (4, q),2.3 (2, t), 1.6 (10, br), 1.5-1.2 (62, m), 1.1 (6, t), 0.9 (6, t)

Purity: >95%

13(14)-hydroxy-14(13)-(nonanoyloxy)docosyl13(14)-hydroxy-14(13)-(nonanoyloxy)docosanoate (C2-II)

Yield: 87.1%

1H-NMR in CDCl₃ (ppm), 4.8 (2, m), 4.1 (2, t), 3.6 (2, br), 2.4-2.3 (6,t), 1.6 (12, br), 1.5-1.2 (86, m), 0.9 (12, t)

Purity: >95%

22-(13(14)-hydroxy-14(13)-(propionyloxy)docosyloxy)-22-oxodocosane-9,10-diyldipropionate or/and22-(13(14)-hydroxy-14(13)-(propionyloxy)docosanoyloxy)docosane-9,10-diyldipropionate(C3)

Pure compound C3 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:10.

Yield: 71.6% C2 and 17.9% C3 at 95° C., 44.8% C4+39.7% C3 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.0 (2, m), 4.8 (1, m), 4.0 (2, t), 3.5 (1, br),2.4-0.22 (8, m), 1.6-1.2 (71, m), 1.1 (9, t), 0.8 (6, t)

Purity: >95%

22-(13,14-bis(propionyloxy)docosanoyloxy)docosane-9,10-diyldipropionate(C4)

Pure compound C4 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:10.

Yield: 44.8% C4+39.7% C3 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.0 (4, m), 4.0 (2, t), 2.4-2.2 (10, m), 1.6-1.4(12, br), 1.4-1.2 (58, m), 1.1 (12, t), 0.8 (6, t)

Purity: >95%

Branched Derivatives of Compound D

Branched Compound D derivatives were prepared from the epoxide ofcompound D and propionic acid at 95° C. for D2 and D3 or 120° C. for D3and D4 (shown in FIG. 9).

14(13)-hydroxy-13(14)-(propionyloxy)docosyl9(10)-hydroxy-10(9)-(propionyloxy)octadecanoate (D2)

Pure compound D2 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:8.

Yield: 77.8% D2+9.5% D3 at 95° C.

1H-NMR in CDCl₃ (ppm), 4.8 (2, m), 4.0 (2, t), 3.6 (2, br), 2.3 (4, q),2.2 (2, t), 1.8-1.5 (10, m), 1.5-1.2 (54, m), 1.1 (6, t), 0.8 (6, t)

Purity: >95%

22-(9(10)-hydroxy-10(9)-(propionyloxy)octadecanoyloxy)docosane-9,10-diyldipropionate or/and1-(14(13)-hydroxy-13(14)-(propionyloxy)docosyloxy)-1-oxooctadecane-9,10-diyldipropionate (D3)

Pure compound D3 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:10.

Yield: 77.8% D2+9.5% D3 at 95° C., 42.8% D4+48.5% D3 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.0 (2, m), 4.8 (1, m), 4.0 (2, t), 3.6 (1, br),2.4-2.2 (8, m), 1.7-1.2 (63, m), 1.1 (9, t), 0.8 (6, t)

Purity: >95%

1-(13,14-bis(propionyloxy)docosyloxy)-1-oxooctadecane-9,10-diyldipropionate (D4)

Pure compound D4 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:10.

Yield: 42.8% D4+48.5% D3 at 120° C.

1H-NMR in CDCl₃ (ppm), 4.8 (4, m), 3.6 (2, t), 2.2-2.0 (10, m), 1.4-1.2(12, br), 1.1-0.9 (50, m), 0.8 (12, t), 0.6 (6, t)

Purity: >95%

Branched Derivatives of Compound E

Branched Compound E derivatives were prepared from the epoxide ofcompound E and propionic acid at 95° C. for E2 and E3 or 120° C. for E3and E4 (shown in FIG. 10).

10(9)-hydroxy-9(10)-(propionyloxy)octadecyl9-hydroxy-10-(propionyloxy)decanoate (E2-1)

Pure compound E2-1 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:4.

Yield: 26% g E3+58% E2-M at 95° C. (E2-M meaning a 70:30 wt:wt mixtureof E2-1 and E2-2 by HPLC).

1H-NMR in CDCl₃ (ppm), 5.0-4.8 (1, m), 4.2 (1, d), 4.1 (2, t), 4.0 (1,dd), 3.8 (1, m), 3.7-3.5 (2, m), 2.4 (4, m), 2.2 (2, t), 1.6-1.2 (41,m), 1.1 (6, m), 0.8 (3, t)

MS (+Na⁺), 623.7

Purity: >95%

10(9)-hydroxy-9(10)-(propionyloxy)octadecyl10-hydroxy-9-(propionyloxy)decanoate (E2-2)

Pure compound E2-2 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:4.

Yield: 26% g E3+58% E2-M at 95° C.

1H-NMR in CDCl₃ (ppm), 5.0-4.8 (1, m), 4.2 (1, d), 4.1 (2, t), 4.0 (1,dd), 3.8 (1, m), 3.7-3.5 (2, m), 2.4 (4, m), 2.2 (2, t), 1.6-1.2 (41,m), 1.1 (6, m), 0.8 (3, t)

Purity: 94.3%

10-(10(9)-hydroxy-9(10)-(propionyloxy)octadecyloxy)-10-oxodecane-1,2-diyldipropionate (E3)

Pure compound E3 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:6 to 1:3.

Yield: 26% g E3+58% E2-M at 95° C., 32.5% E4+21.5% E3+33.7% E2 at 120°C.

1H-NMR in CDCl₃ (ppm), 5.1 (1, m), 4.8 (1, m), 4.2 (1, d), 4.0 (3, m),3.6 (3, br), 2.3 (8, m), 1.7-1.2 (41, m), 1.1 (9, m), 0.8 (3, t)

Purity: >95%

1-(9,10-bis(propionyloxy)decanoyloxy)octadecane-9,10-diyl dipropionate(E4)

Pure compound E4 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:6.

Yield: 32.5% E4+21.5% E3+33.7% E2 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.1 (1, m), 5.0 (2, m), 4.2 (1, d), 4.0 (3, m),2.3 (10, m), 1.7-1.5 (10, m), 1.4-1.2 (30, m), 1.1 (12, m), 0.8 (3, t)

Purity: >95%

Branched Derivatives of Compound F

Branched Compound F derivatives were prepared from the epoxide ofcompound F and propionic acid at 95° C. for F2 and F3 or 120° C. for F3and F4 (shown in FIG. 11).

9-hydroxy-10-(propionyloxy)decyl9(10)-hydroxy-10(9)-(propionyloxy)octadecanoate (F2-1)

Pure compound F2-1 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:4.

Yield: 19.8% F3+64.3% F2-M from 3.2 g

1H-NMR in CDCl₃ (ppm), 5.0-4.8 (1, m), 4.2 (1, d), 4.1 (2, t), 4.0 (1,dd), 3.8 (1, m), 3.7-3.5 (2, m), 2.4 (4, m), 2.2 (2, t), 1.6 (8, m),1.6-1.2 (33, m), 1.1 (6, m), 0.8 (3, t)

Purity: >95%

10-hydroxy-9-(propionyloxy)decyl9(10)-hydroxy-10(9)-(propionyloxy)octadecanoate (F2-2)

Pure compound F2-2 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:4.

Yield: 19.8% F3+64.3% F2-M

1H-NMR in CDCl₃ (ppm), 5.0-4.8 (1, m), 4.2 (1, d), 4.1 (2, t), 4.0 (1,dd), 3.8 (1, m), 3.7-3.5 (2, m), 2.4 (4, m), 2.2 (2, t), 1.6 (8, m),1.6-1.2 (33, m), 1.1 (6, m), 0.8 (3, t)

Purity: >95%

10-(9(10)-hydroxy-10(9)-(propionyloxy)octadecanoyloxy)decane-1,2-diyldipropionate (F3)

Pure compound F3 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:6.

Yield: 19.8% F3+64.3% F2-M at 95° C., 51.3% F4+30% F3 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.1 (1, m), 4.8 (1, m), 4.2 (1, d), 4.0 (3, m),3.7 (3, br), 2.3 (8, m), 1.6 (8, m), 1.5-1.2 (33, m), 1.1 (9, m), 0.8(3, t)

MS (+Na⁺), 679.3

Purity: >95%

1-(9,10-bis(propionyloxy)decyloxy)-1-oxooctadecane-9,10-diyldipropionate (F4)

Pure compound F4 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:6.

Yield: 51.3% F4+30% F3 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.1 (1, m), 5.0 (2, m), 4.2 (1, d), 4.0 (3, m),2.3 (10, m), 1.7-1.4 (10, m), 1.4-1.2 (30, m), 1.1 (12, m), 0.8 (3, t)

MS (+Na⁺)735.6

Purity: >95%

Branched Derivatives of Compound G

Branched compound G derivatives were prepared from the epoxide ofcompound G and propionic acid at 95° C. for G2 and G3 or 120° C. for G3and G4 (shown in FIG. 12).

9-hydroxy-10-(propionyloxy)decyl 9-hydroxy-10-(propionyloxy)decanoate(G2-1)

Pure compound G2-1 was given as white solid by column chromatographywith Ethyl acetate/Hexane=1:2.

Yield: 47.7% G3+51.2% G2-M at 95° C.

1H-NMR in CDCl₃ (ppm), 4.9 (1, br), 4.2 (2, d), 4.0 (2, m), 3.9 (2, dd),3.8 (2, br), 3.7-3.6 (1, m), 2.4 (4, m), 2.2 (2, t), 1.6 (5, m), 1.5 (4,m), 1.4-1.2 (17, m), 1.1 (6, t)

Purity: >95%

10-hydroxy-9-(propionyloxy)decyl 9-hydroxy-10-(propionyloxy)decanoateor/and 9-hydroxy-10-(propionyloxy)decyl10-hydroxy-9-(propionyloxy)decanoate (G2-2)

Pure compound G2-2 was given as white solid by column chromatographywith Ethyl acetate/Hexane=1:2.

Yield: 47.7% G3+51.2% G2-M at 95° C.

1H-NMR in CDCl₃ (ppm), 4.9 (1, br), 4.2 (2, d), 4.0 (2, m), 3.9 (2, dd),3.8 (2, br), 3.7-3.6 (1, m), 2.4 (4, m), 2.2 (2, t), 1.6 (5, m), 1.5 (4,m), 1.4-1.2 (17, m), 1.1 (6, t)

MS (+Na⁺):511.3

Purity: >95%

10-(9-hydroxy-10-(propionyloxy)decanoyloxy)decane-1,2-diyl dipropionateor/and 10-(9-hydroxy-10-(propionyloxy)decyloxy)-10-oxodecane-1,2-diyldipropionate (G3-1)

Pure compound G3-1 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:3.

Yield: 47.7% G3+51.2% G2-M at 95° C., 57.2% G4+21.5% G3 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.1 (1, br), 4.2 (1, d), 4.1 (1, d), 4.0 (2, m),3.9 (2, dd), 3.8 (1, br), 2.3 (8, m), 1.7-1.2 (27, m), 1.1 (9, m)

Purity: >95%

10-(10-hydroxy-9-(propionyloxy)decanoyloxy)decane-1,2-diyl dipropionateor/and 10-(10-hydroxy-9-(propionyloxy)decyloxy)-10-oxodecane-1,2-diyldipropionate (G3-2)

Pure compound G3-2 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:3.

Yield: 47.7% G3+51.2% G2-M at 95° C., 57.2% G4+21.5% G3 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.1 (1, br), 4.2 (1, d), 4.1 (1, d), 4.0 (2, m),3.9 (2, dd), 3.8 (1, br), 2.3 (8, m), 1.7-1.2 (27, m), 1.1 (9, m)

Purity: >95%

10-(9,10-bis(propionyloxy)decanoyloxy)decane-1,2-diyl dipropionate (G4)

Pure compound G4 was given as colorless oil by column chromatographywith Ethyl acetate/Hexane=1:5.

Yield: 57.2% G4+21.5% G3 at 120° C.

1H-NMR in CDCl₃ (ppm), 5.1 (2, m), 4.2 (2, d), 4.0 (4, m), 2.3 (10, m),1.6 (7, m), 1.5 (18, m) 1.1 (12, m)

Purity: >95%

Synthesis of (E)-didec-9-enyl octadec-9-enedioate and its branchedcompounds (Compound H) Materials:

Oleic acid (90%), Grubbs metathesis catalyst (2^(nd) generationcatalyst), 9-decen-1-ol, Propionic acid, Chloroform, Dichloromethane,N,N′-Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP),Formic acid, hydrogen peroxide were purchased from Sigma-Aldrich. Hexaneand Ethyl Acetate from ACP Chemical Int. (Montreal, Quebec, Canada) wereused without further treatment. The synthesis procedure for compound His shown in FIG. 13.

E-didec-9-enyl octadec-9-enedioate was prepared from 9-decen-1-ol and1,18-Octadec-9-enedioic acid which was prepared from Oleic acid bymetathesis reaction with Grubbs catalyst (2^(nd) generation).

Synthesis of 1,18-Octadec-9-enedioic acid

Oleic acid (76 g (270 mmol)) was transferred into a 250 ml three-neckedround bottomed flask and stirred at a temperature typically between10-100° C., preferably between about 30-70° C., and most preferably at45° C. under nitrogen gas for 0.5 h. Grubbs metathesis catalyst 2^(nd)generation (85 mg) was added. The reaction mixture was stirred at 45° C.for around 5 min, at which point diacid (1,18-Octadec-9-enedioic acid)began to be precipitated from the reaction mixture. The reaction waskept at this temperature for 24 hours and then it was quenched withethyl vinyl ether (15 ml), and excess ether was removed under reducedpressure. The residue was purified by recrystallization from ethylacetate and hexane (1:2) to give 29.75 g of product as a white solid.

Yield: 72%

¹H-NMR in DMSO-d6 (ppm): 12 (2H, s, —COOH), 5.3 (2H, t, —CH═CH—), 2.2(4H, m, —CH2-COOH), 1.9 (4H, m, —CH2-CH═), 1.4 (4H, m, —CH2-CH2-COOH),1.3-1.2 (18H, m, CH2)

Purity: >95%

Synthesis of (E)-didec-9-enyl octadec-9-enedioate (H)

To the solution of 1,18-Octadec-9-enedioic acid (15.6 g, 50 mmol) and9-decen-1-ol (23.4 g, 150 mmol) in CHCl₃ at around 0° C., DMAP (12.2 g,100 mmol) was added, followed by slow addition of DCC (22.7 g, 110mmol). The reaction mixture was allowed to be warmed to room temperatureand kept overnight. The mixture was filtered to remove solid. Thefiltrate was concentrated on a rotary evaporator. The residue waspurified by flash chromatography using Ethyl acetate/Hexane (1:40) togive 28 g of product as a colorless oil.

¹H-NMR in CDCl₃ (ppm): 5.8 (2H, m, ═CH—), 5.4 (2H, t, —CH═CH—), 5.0-4.8(4H, dd, CH2=), 4.0 (4, t, —CH2-O), 2.3 (4H, t, O═C—CH2-), 2.1-1.8 (8H,m, ═CH—CH2-), 1.6 (8H, m, —CH2-CH2-O—), 1.4-1.2 (36, m, —CH2-)

Purity: >95%

Epoxidation of H (FIG. 14)

To a stirred solution of ester (2.7 g, 4.56 mmol) and formic acid (2.2g, 9 mmol) in 3 mL CH₂Cl₂ at 4° C., H₂O₂ (30%) (3.4 g, 6.6 mmol) wasslowly added. The reaction proceeded at room temperature with vigorousstirring for 48 hrs. After removal of the water phase, more CH₂Cl₂ (10mL) was added to organic phase, which was washed sequentially with water(2×20 mL) sat. aq NaHCO₃ (2×10 mL) and brine (2×20 mL), dried on Na₂SO₄,filtered, and concentrated on a rotary evaporator. The residue waspurified by column chromatography with Ethyl acetate/Hexane=1:4 to give2.1 g of white solid.

Yield: 72%

¹H-NMR in CDCl₃ (ppm): 4.0 (4H, t, —CH2-O—), 2.9 (2H, m,), 2.7 (2H, t),2.6 (2H, t), 2.4 (2H, dd), 2.3 (4H, t, O═C—CH2-), 1.7-1.2 (52H, m)

Purity: >95%

Synthesis of Branched Compounds of Compound H (FIG. 14)

The branched compounds below are referred to as H3 (3-branched), H4(4-branched), H5 (5-branched), and H6 (6-branched). To the epoxidationproducts above (1.6 g, 4.7 mmol), 15.47 mmol propionic acid was added.The reaction was carried out under an N₂ atmosphere and heated totypically between 50-150° C., preferably between about 70-120° C., andmost preferably at 95° C. and stirred at 95° C. for typically betweenabout 4 to 36 hours, preferably 10-20 hours, and most preferably 16hours. To achieve 5 or 6 branches in the compounds, the reactiontemperature was raised to typically between 60-160° C., preferablybetween about 80-140° C., and most preferably at 120° C. The resultingproducts were poured into 10 ml of water and extracted with Ethylacetate (2×10 mL). The organic phase was washed sequentially by water(2×10 mL), sat. aq NaHCO₃ (2×10 mL) and brine (2×20 mL), dried onNa₂SO₄, then filtered and concentrated on a rotary evaporator. Theresidue was purified by column chromatography with Ethyl Acetate/Hexane(1:1 for H3, 1:2 for H4, 1:3 for H5 and 1:4 for H6).

Yield: 37.5% H3+43.8% H4+11.5% H5 at 95° C., and 43.7% H5+38.4% H6 at120° C.

¹H-NMR in CDCl₃ (ppm)

1-(9(10)-hydroxy-10(9)-(propionyloxy)decyl)18-(10(9)-hydroxy-9(10)-(propionyloxy)decyl)-9(10)-hydroxy-10(9)-(propionyloxy)octadecanedioate(H3)

5.1-4.8 (2H, m), 4.3-4.1 (2H, dd), 4.0 (4H, t), 4.0-3.9 (2H, dd), 3.8(1H, m), 3.7-3.5 (2H, m), 2.4-2.2 (10H, m), 1.9 (3H, br, —OH), 1.6-1.2(52H, m), 1.2-1.0 (9H, t, —CH3).

MS (M+Na⁺): 881.5

Purity: >95%

1-(9,10-bis(propionyloxy)decyl)18-(9(10)-hydroxy-10(9)-(propionyloxy)decyl)10(9)-hydroxy-9(10)-(propionyloxy)octadecanedioate (H4)

5.2-4.8 (3H, m), 4.3-4.1 (2H, dd), 4.0 (4H, m), 4.0-3.9 (1, dd), 3.8(1H, m), 3.7-3.5 (2H, m), 2.4-2.2 (12H, m), 1.9 (2H, br, —OH), 1.7-1.2(52H, m), 1.1 (12H, m, —CH3).

MS (M+Na⁺): 937.6

Purity: >95%

Bis(9,10-bis(propionyloxy)decyl)9(10)-hydroxy-10(9)-(propionyloxy)octadecandioate(H5)

5.2-4.7 (3H, m), 4.2 (2H, dd), 4.0 (6H, m), 3.6 (1H, m), 2.3 (14H, m),1.6-1.4 (16, m), 1.4-1.2 (36H, m), 1.1 (15, m)

MS (M+Na⁺): 993.9

Purity: >95%

Bis(9,10-bis(propionyloxy)decyl)9,10-bis(propionyloxy)octadecanedioate(H6)

5.1 (2H, m), 4.9 (2H, m), 4.2 (2, dd), 4.0 (6H, q), 2.3 (16H, m),1.7-1.4 (16H, m), 1.4-1.2 (36H, m), 1.1 (18, m)

MS (M+Na⁺): 1049.9

Purity: >95%

Composition of Crude Samples

Several compounds described herein are crude samples, as in they aremixtures of existing branched derivatives of a dimer and/or trimerester. Compounds E95, F95, G95, and H95 are the crude samples ofcompounds E F, G, and H, respectively. These are mixtures of branchedcompounds of compounds E F, G, and H, respectively, which were preparedfrom their epoxides and propionic acid at 95° C. Reaction time for thesecompounds was 24 hours. Similarly, compounds E120, F120, and G120 arecrudes of compounds E, F, and G, respectively, prepared at 120° C. for24 hours. H120A is the crude sample of compound H prepared at 120° C.for 16 hours. H120 B is the crude sample of compound H prepared at 120°C. for 26 hours. As referred to at a later point in this application,H120C is the crude sample of compound H prepared at 120° C. for 26hours, and H120-20H is the crude sample of compound H prepared at 120°C. for 20 hours. The Table 4 below summarizes the specific compositionsof the above crude samples. Also in Table 4 below, “NI” means “notidentified.”

TABLE 4 Compositions of H branched compounds (%) Name H3 H4 H5 H6 NIwater H95 (26 hours) 37.48 43.83 11.69 0 7 — H120A (16 hours) 6.31 39.6635.82 6.14 3.72 8 H120B (26 Hours) 0 7.12 33.7 38.43 20.75 — 120A Dry7.23 43.11 38.94 6.67 4.05 — Compositions of E branched compounds NameE2 E3 E4 NI — — E95 88.06 11.39 — — — — E120 6.46 77.83 15.7 — — —Compositions of G branched compounds Name G2 G3 G4 NI — — G95 30.6656.97 12 — — — G120 3.5 44.52 51.08 — — — Compositions of F branchedcompounds Name F2 F3 F4 NI — — F95 85.43 12.82 — 1.75 — — F120 39.1253.01 4.28 3.60 — —

Study of Time and Temperature Dependence of the Ring-Opening Reaction ofEpoxides by Propionic Acid

Exhaustive efforts were made to synthesize pure samples of the baseesters A-H and their individual branched derivatives, so as tounderstand the influence of structure on lubrication and low temperaturefluidity properties. In this section, the mixture of branched productsarising out of the epoxide of certain base esters (compounds E, G, andH), was studied by controlling the temperature of the ring-openingreaction and quenching the reaction at various time periods (asgenerically shown in FIG. 15).

By managing the degree of ring opening, the structure of the complexester mixture is altered so that the low temperature properties of thefluids are adjusted to best fit various applications. Due to theirasymmetric structures and terminal epoxide rings, the ring-openingesterification of compounds E, G, and H derivatives are complex. Inorder to optimize the reaction conditions and better control thering-opening esterification, so as to produce an optimized mixture ofstructures in the complex ester mixture which then delivers uniquefunctionality for specific applications, it is important to understandthe time-temperature dependence of the reaction.

Materials:

Compounds E, G, and H were prepared from Oleic acid, 9-decenoic acid and9-decen-1-ol as detailed above; Propionic acid, H₂O₂, and Formic acidwere purchased from Sigma-Aldrich. FIGS. 16-18 show the reactions thatwere being performed, to varying degrees, for compounds E, G, and H.

Method:

The epoxides were prepared from esters of E, G, and H, followed byring-opening reactions with propionic acid using solvent-freeconditions, as described above. The reactions were carried out at 95° C.and 120° C. for 24 hours and at 140° C. for 8 hours. HPLC-ELSD was usedto monitor the ring-opening reactions.

The samples were measured on Waters e2695 HPLC with Waters 2424 ELSDetector and C18 column (5 um 4.6×150 mm). The mobile phase was mixtureof 85% ACN: 15% water with a flow rate of 1 mL/min. The individual purebranched derivatives were first used as standards, so that the complexmixtures could be analyzed with confidence.

The following Tables 5 through 13 show the evolution of the variousbranched species of several base esters with time at the varioustemperatures. These complex mixtures were also analyzed for lubricatingand low temperature fluidity and the structure-function relationshipsexamined, separately below.

Tables 5 through 13: Time-Temperature dependence of ring openingreactions

TABLE 5 Composites of ring-opening of epoxide of G at 95° C. Time(hours) G2 G3 G4 SM G1R 0.00 100.00 1.00 3.14 0.00 0.00 58.63 38.23 2.0020.25 0.00 0.00 21.51 58.23 4.00 64.71 5.57 0.00 5.57 29.70 6.00 81.268.08 0.00 0.00 10.66 8.00 79.35 16.73 0.00 3.64 11.00 69.94 27.82 1.230.67 13.00 61.69 35.52 2.13 0.26 24.00 30.66 56.97 12.00

TABLE 6 Composites of ring-opening of epoxide of G at 120° C. Time(hours) G2 G3 G4 SM G1R 0.00 100.00 1.00 27.63 16.96 0.00 16.91 54.972.00 73.54 18.63 0.00 7.25 18.63 4.00 66.16 31.58 1.85 0.41 6.00 44.1148.82 7.06 8.00 29.00 57.26 13.66 11.00 13.52 57.18 29.00 24.00 0.6921.34 76.38

TABLE 7 Composites of ring-opening of epoxide of G at 140° C. Time(hours) G2 G3 G4 SM G1R 0.00 100.00 0.50 51.92 6.27 41.46 1.00 82.147.28 7.28 2.00 68.41 29.89 1.39 0.17 3.00 45.12 49.11 5.59 4.00 33.0156.70 10.13 5.00 24.68 58.99 16.16 6.00 14.96 58.04 26.80 7.00 4.7345.94 49.13 8.50 3.50 44.52 51.08

TABLE 8 Composites of ring-opening of epoxide of H at 95° C. Time(hours) H3 H4 H5 H2R H1R SM 0.00 100.00 1.00 11.30 88.70 2.00 0.26 40.836.23 52.68 3.00 2.03 51.13 19.07 27.77 5.00 11.56 37.00 43.49 7.95 7.0026.25 2.76 18.08 46.89 6.03 9.00 40.93 6.69 8.45 39.89 3.96 13.00 55.1816.31 3.76 20.44 4.31 26.00 37.48 43.84 11.48 3.28 7.90 2.26

TABLE 9 Composites of ring-opening of epoxide of H at 120° C. Time(hours) H3 H4 H5 H6 H2R H1R SM 0.00 100.00 1.00 8.20 40.28 42.74 8.782.00 40.06 4.88 42.29 8.69 4.08 3.00 59.50 14.43 18.51 2.64 4.29 5.0050.58 36.29 5.23 3.19 2.22 2.48 7.00 30.80 49.95 14.95 0.96 2.19 1.149.00 20.83 50.30 23.62 2.54 2.72 12.00 9.16 41.74 37.44 6.13 24.00 9.4646.53 33.65 26.00 7.12 43.70 38.43

TABLE 10 Composites of ring-opening of epoxide of H at 140° C. Time(hours) H3 H4 H5 H6 H1R H2R SM 0.00 100.00 0.50 2.86 36.22 54.11 6.821.00 61.51 38.49 1.50 81.74 9.70 8.56 2.00 73.78 23.71 2.51 3.00 59.5940.41 4.00 37.82 59.91 2.26 5.00 25.59 66.87 6.48 6.00 20.81 70.13 9.067.00 15.70 68.76 14.11 0.91 8.00 10.20 67.08 19.66 1.89 24.00 12.0952.74

TABLE 11 Composites of ring-opening of epoxide of E at 95° C. Time(hours) E2 E3 E4 E1R1 E1R1 SM 0.00 100.00 1.00 1.09 18.09 5.00 75.702.00 13.71 44.17 11.09 31.03 4.00 57.75 33.68 6.22 2.34 6.00 81.04 17.341.62 8.00 91.64 1.53 6.83 10.00 95.15 2.44 2.42 12.00 95.27 4.73 24.0088.06 11.39

TABLE 12 Composites of ring-opening of epoxide of E at 120° C. E2 E3 E4E1R1 E1R2 SM 0.00 100.00 0.50 13.12 43.04 9.82 34.02 1.00 68.50 27.853.65 2.00 95.91 4.20 3.00 97.52 2.48 4.00 94.21 5.79 6.00 87.99 12.008.00 69.72 30.28 10.00 59.35 40.65 12.00 44.31 55.02 0.67 24.00 6.4677.83 15.70

TABLE 13 Composites of ring-opening of epoxide of E at 140° C. Time(hours) E2 E3 E4 E1R1 E1R2 SM 0.00 100.00 0.50 82.47 19.54 0.00 1.00100.00 1.50 96.45 3.55 2.00 91.43 8.57 3.00 74.33 25.66 4.00 61.90 48.106.00 20.70 74.80 4.50 7.50 9.63 81.50 8.87

II. Experimental Methods—Measurement of Physical Properties

For the synthesized dimer esters and trimer esters (compounds A-H), andtheir respective branched derivatives described above, the followingdescribes the experimental methods utilized to measure physicalproperties of the aforesaid compounds.

Differential Scanning Calorimetry

The cooling and heating profiles of all compounds were carried out usinga Q200 model DSC (TA Instruments, DE, USA) equipped with a refrigeratedcooling system (RCS 90, TA Instrument).

Approximately 5.0-10.0 (±0.1) mg of fully melted and homogenously mixedsample was placed in an aluminum DSC pan which was then hermeticallysealed. An empty aluminum pan was used as a reference and themeasurements were performed under a nitrogen flow of 50 mL/min.

The “TA Universal Analysis” software coupled with a published method(Use of first and second derivatives to accurately determine keyparameters of DSC thermographs in lipid crystallization studies.Thermochimica Acta, 2005. 439(1-2): p. 94-102, Bouzidi et al., 2005) wasused to analyze the data and extract the main characteristics of thepeaks (temperature at maximum heat flow, T_(m); onset temperature,T_(On); offset temperature, T_(Off); enthalpy, AH; and full width athalf maximum, FWHM). The temperature window over which a thermal eventoccurs is defined as the absolute value of the difference betweenT_(Off) and T_(On) of that event. It is labeled ΔT_(C) forcrystallization and ΔT_(M) for melting. The characteristics of theshoulders when present were estimated using a simple decomposition ofthe signal into its obvious main components. The positions in this casewere estimated using the first and second derivatives of thedifferential heat flow.

The samples were subjected to cooling profiles which allow forcomparison between the different techniques used. The samples wereheated to 50° C. and held for 5 min, a temperature and a time over whichcrystal memory is erased, and then cooled at a constant rate of 3.0°C./min, to a finish temperature of −90° C., where it was heldisothermally for a 5 min. The sample was then reheated at a constantrate of 3.0° C./min to 70° C. to obtain the melting profile.

In some instances (E2-2, E2-M, F2-1, F2-2, F3, F4), a 0.1° C./mincooling rate was used. The sample in this case was heated to 90° C. andheld for 5 min and then cooled at the constant rate down to −90° C.where the sample was held isothermally for 5 min then reheated to 90° C.at a constant rate of 3.0° C./min to obtain the heating profile.

Thermo Gravimetric Analysis

The TGA measurements were carried out on a TGA Q500 (TA Instruments, DE,USA) equipped with a TGA heat exchanger (P/N 953160.901). Approximately8.0-15.0 mg of fully melted and homogenously mixed sample was loaded inthe open TGA platinum pan. The sample was heated from 25 to 600° C.under dry nitrogen at a constant heating rate of 3° C./min. The TGAmeasurements were performed under a nitrogen flow of 40 mL/min forbalance purge flow and 60 mL/min for sample purge flow. All the sampleswere run in triplicate.

The samples which were run by TGA are: A, B, C, D, A2, C2, E2 G4, H5,H6, E, F, G, E95, E120, F95, F120, G95, G120, G140, H95, H120A, andH120B.

Viscosity Measurement

Sample viscosities were measured on a computer-controlled rheometer,AR2000ex, equipped with a standard AR Series Peltier Plate and PeltierAR series Concentric Cylinder (TA Instruments, DE, USA). The circulatingfluid heat exchange medium was provided either by a TA heat exchanger(TA P/N 953/160.901) or a temperature controlled circulating water bath(Julabo F25, Allentown, Pa.). The AR Series Peltier Plate has a 80-mmdiameter hardened chrome surface and can provide a continuoustemperature range of −20° C. to 180° C. when used with circulating waterat 1° C. and −40° C. to 160° C. when an appropriate circulating fluid at−20° C. is used. The AR Series Peltier concentric cylinder can provide acontinuous temperature range of 0° C. to 100° C. when used withcirculating water at 1° C. and −40° C. to 100° C. when an appropriatecirculating fluid at −20° C. is used. The internal resolution of bothsystems is 0.01° C. The AR Series plate and cylinder offer typicalheating rates of up to 50 and 13° C./min, respectively and a temperatureaccuracy of 0.1° C.

The experiments were performed under an air bearing pressure at 27 psi.A 40-mm 2° steel cone (SIN 511406.901) geometry was used for testinghigh viscosity materials and a standard-size recessed-end concentriccylinder (stator inner radius 15 mm and rotor outer radius 14 mm, SIN545023.001) for low viscosity materials. Approximately 0.59 mL and 6.65mL of fully melted and homogenously mixed sample was used in theparallel plate and concentric cylinder geometry, respectively.Circulating water at 0° C. in the TA heat exchanger and 6° C. in thecirculating bath were used and temperatures as low as −10° C. and ashigh as 120° C. were easily obtained with an accuracy of 0.1° C.

Viscosities of samples were measured from temperatures above eachsample's melting point up to 110° C. The measurements were performedusing 3 methods: 1. Shear rate/share stress curves, 2. ConstantTemperature Rate, Constant shear rate procedure, and 3. Peak holdprocedure. The viscosities measured viscosities were found in goodagreement within experimental uncertainty.

Shear Rate/Share Stress Curves (Increasing and Decreasing Shear Rate)

The procedure was carried out by controlling shear rate, andmeasurements were performed in 10° C. steps. The shear rate range wasoptimized for torque (lowest possible is 10 μNm) and velocity (maximumsupplier suggested of 40 rad/s). At each measurement temperature, thelowest shear rate accessible was determined by controlling the lowesttorque available compatible with the temperature, and the highest shearrate was determined by increasing the applied torque to a level wherethe maximum suggested velocity is reached. Typical optimization resultsare summarized in Table 14 below.

TABLE 14 Typical optimized shear rate limits for different temperaturesof measurements. shear rate (s⁻¹) Temperature Upper (° C.) Lower limitlimit 110 100 1200 100 50 1200 90 10 1200 80 10 1200 70 10 1200 60 11200 50 1 1200 40 1 1200 30 0.5 1200 20 0.1 1200 10 0.1 700 0 0.01 700−10 0.01 500

We have used three (3) available shear rate/share stress procedures todetermine viscosity:

Continuous Ramp Procedure:

The sample was first heated to 110° C. and equilibrated for 5 min and acontinuous ramp procedure was initiated from 110° C. down to the meltingtemperature by 10° C. steps. The procedure is repeated for eachtemperature with 5 min equilibration time at each temperature. Shearrate was increased from lower to upper shear rate according to Table 14.Duration was 10 min in the log mode and sampling was 20 point perdecade. G4 was also run with decreasing shear rate to allow forcomparison.

Steady State Flow Procedure:

This procedure was used for a limited number of samples (which are E2-2,E95, E120, F95, F120, G95, G120, H95, H120A, H120A_dry, H120B, H3, H4,H5 and H6) for comparison and optimization purposes. The sample was alsoheated to 110° C. and equilibrated for 5 min and the continuous rampprocedure was initiated down to the melting temperature by 5° C. steps.The procedure is repeated for each temperature with 5 min equilibrationtime at each temperature. Increasing shear rate from the lower limit tothe upper limit was used in the linear mode with 25 s⁻¹ steps andsampling period of 1 min.

Step Flow Procedure

The step flow procedure was only used for one sample (G3-1). The samplewas first measured at its melting point (0° C.) then at increasingtemperatures (10° C. steps). The sample was equilibrated for 5 min atthe measurement temperature and then subjected to the step flowprocedure using 20 sampling points per decade, a constant time of 30 s,and average last 10 seconds. Shear rate was increased from its lower toits upper limit according to Table 14.

Constant Temperature Rate Procedure

In order to speed up data collection, cooling and heating rateprocedures were tested and compared to the shear rate/shear stressprocedure. The sample was quickly heated to 110° C. and equilibrated atthis temperature for 5 min then cooled down at a constant rate (3.0°C./min) to its melting temperature. A constant shear rate of 200 s⁻¹ waschosen as it was the lowest common shear rate which yielded a constantviscosity in the range applied (Newtonian behavior—characterized byhaving a shear stress that is linearly proportional to the shear strainrate) as determined from the continuous ramp procedure. Sampling pointswere recorded every 1° C. All other measurement conditions were keptconstant.

Some samples (E2-2, F2-2, G3-1, H120B) were run using decreasingtemperature ramp at the same conditions. Other samples (E2-2, G3-1, E95,E120, F120, G95, G120, H95, H120A, H120A_dry, H120B, H3, H4, H5 and H6)were run at decreasing temperature using a rate of 1.0° C./min. G3-1 wasalso run at increasing temperature using a rate of 1.0° C./min.

Peak Hold Procedure

The peak hold procedure is an alternative to the constant rateprocedure. It also uses a fixed shear rate and is based on theequilibration and holding of the sample at a set temperature,measurement of viscosity and subsequent stepping the temperature foranother equilibration, holding and measurement. This procedure was usedonly for one sample (G3-1) and was found comparable and therefore wasnot employed further. The procedure was started at the sample meltingpoint (−1° C.) and 3 C steps with 5 min equilibration and 10 minduration time. A shear rate of 200 s⁻¹ was used.

III. Properties of the Compounds of this Invention

The dimer and trimer esters and their branched derivatives of thepresent invention exhibit improved viscosity at the full range ofoperating conditions, improved oxidative stability (meaning removal ofdouble bonds in the case of natural oil derived materials), and improvedthermal stability. In particular, we have discovered that in thebranched derivatives, branching the hydrocarbon backbone in anasymmetrical fashion greatly improves low temperature performance, andhas improved fluidity at low temperatures in an unexpected manner. Theseaspects are described in further detail below.

Table 15 below shows the crystallization onsets, onsets and offsets ofmelt (all in ° C.), and dynamic viscosities at 0° C., 20° C., 40° C.,and 100° C. (in m-Pascal-seconds, or mPa·s), of all the compoundscreated in this invention.

TABLE 15 Crystallization onsets, onsets and offsets of melt (all in °C.), and dynamic viscosities at 0° C., 20° C., 40° C., and 100° C. (inmPa · s), of all the compounds created in this invention. Melting FinalCrystallization Onset Melting Viscosity at Viscosity at ViscosityViscosity Sample Onset (° C.) STD (° C.) STD Offset (° C.) STD 0° C. 20°C. at 40° C. at 100° C. A −0.69 0.26 −12.29 0.05 10.01 0.07 90 29.8 16.05.2 A2 −37.67 1.02 −57.81 0.36 −40.27 0.16 12210 1706.0 391.1 27.5 A2-II−27.40 0.35 −20.32 0.32 29.18 0.34 N/A N/A N/A N/A A3 −48.70 1.09 −68.570.04 −53.55 0.51 3850 712.0 199.5 20.8 A4 −55.00 5.44 −72.71 0.40 −61.990.10 1876 407.4 129.9 17.0 B 15.20 1.57 0.58 0.09 16.84 0.84 Not Liquid40.7 20.9 5.9 B2 −34.66 0.07 −32.87 0.03 50.36 1.24 13000 1846.0 426.029.8 B3 −43.02 0.05 −57.54 0.28 −34.74 0.55 3970 710.9 236.3 23.3 B4−50.90 3.50 −72.14 0.04 −39.58 1.22 2192 479.3 152.1 19.9 C 25.97 0.9314.84 0.40 30.42 0.74 Not Liquid Not Liquid 28.0 7.5 C2 −14.79 0.10−12.01 0.15 51.99 0.05 15030 2156.0 500.8 33.5 C2-II −5.03 0.59 −4.350.59 3.88 0.15 N/A N/A N/A N/A C3 −36.10 0.36 −35.37 0.83 −4.99 0.233912 78.0 227.2 24.3 C4 −50.00 0.80 −70.43 0.07 −12.49 0.15 2512 559.8177.9 29.5 D 14.41 3.01 2.77 0.15 23.55 2.35 Not Liquid 40.3 21.0 5.9 D2−37.90 0.04 −41.15 0.04 −28.21 0.32 13860 1959.0 451.5 30.7 D3 −51.500.50 −66.38 2.15 −39.37 1.49 4092 777.6 221.8 22.8 D4 −50.10 5.00 −71.170.04 −61.42 0.00 2330 507.3 160.3 19.8 E −13.35 0.14 −13.61 0.21 −6.470.08 Not Liquid 7.5 4.8 2.2 E2-1 −25.56 4.05 −67.54 0.06 27.48 0.22 4648824.6 221.0 26.8 E2-2 −36.14 0.73 −62.39 0.20 −51.23 0.55 7414 1175.0289.7 23.2 E2-M −42.26 1.32 −62.86 0.16 −25.67 0.04 7279 1188 300.6 28.6E3 −50.83 1.83 −75.23 0.50 −60.08 0.70 2044 424 130.4 16.0 E4 −36.8425.00 −76.09 0.13 −68.94 0.16 1012 241.6 83.6 13.1 F −5.79 0.02 −19.530.00 5.81 0.24 Not Liquid 9.049 5.7 2.3 F2-1 −14.74 0.09 −67.22 0.3441.60 0.03 5939 1010 260.2 21.8 F2-2 −40.91 1.26 −61.04 0.31 −50.77 0.395003 877 232.0 29.6 F2-M −28.58 0.47 −63.05 0.48 32.90 0.30 5792 984.7255.9 22.1 F3 −56.84 1.68 −77.17 1.22 −61.34 0.69 2013 419.3 129.6 17.3F4 −47.05 20.00 −84.92 0.19 −74.34 0.73 698 179.7 66.4 11.6 G −19.470.77 −18.30 0.11 −14.70 0.28 Not Liquid 2.409 1.7 1.0 G2-1 36.76 1.79−80.35 0.54 54.66 0.02 Not Liquid Not Liquid 170.2 19.0 G2-2 −8.08 0.03−73.68 0.98 29.16 0.24 N/A N/A N/A N/A G2-M 19.28 0.20 −24.48 0.71 43.410.17 Not Liquid Not Liquid 183.3 21.5 G3-1 −21.77 0.18 −78.56 0.76−15.60 0.07 928 224.2 78.3 11.3 G3-2 −50.63 0.98 −73.39 0.05 −37.22 0.34N/A N/A N/A N/A G3-M −33.85 0.21 −74.73 0.20 −25.46 0.21 1523 341.6113.2 16.0 G4 No crystallization up to −90° C. 379 105.8 43.4 7.9 H18.76 1.10 22.27 0.12 24.94 0.40 Not Liquid Not Liquid 25.4 7.1 H3−26.71 0.10 −61.49 0.13 33.96 0.64 23350 3304.0 773.0 56.1 H4 −34.732.94 −64.37 0.12 29.66 0.50 9575 1589.0 420.1 38.9 H5 −51.78 0.36 −68.100.21 12.35 0.35 4691 891.7 260.3 28.3 H6 −49.80 0.82 −71.10 0.36 −20.341.24 3399 684.7 210.3 27.5 E95 −1.95 0.05 −67.96 0.05 16.41 0.11 3363627.9 177.9 21.0 E120 −10.02 0.07 −72.74 0.16 −2.29 0.81 1796 385.7121.3 N/A F95 −33.83 0.16 −66.35 0.06 28.32 0.34 Not Liquid 721.3 198.820.8 F120 −53.44 0.42 −69.94 0.32 −24.75 0.15 2751 538.2 157.7 17.2 G95−8.73 0.47 −76.68 0.41 7.97 0.43 1853 408.2 133.4 18 G120 −44.38 0.34−78.41 0.01 −23.71 0.37 833.1 203.7 73.2 12 H95 −25.90 0.37 −63.33 0.3413.47 0.44 N/A 2189 554.6 45.3 H120A −56.52 2.48 −74.74 0.09 −64.64 0.796999 1259 346.5 36.06 H120A −43.57 2.09 −66.48 0.21 −58.21 0.19 78231371 378.4 36.7 Dry H120B −49.71 1.97 −68.11 0.05 −59.75 0.09 5752 1064306.8 32.4 N/A = Not Available.

Several of the compounds in this invention have superior melt onsetscompared to the cited prior art efforts. The onsets of melt, and dynamicviscosities at 40° C. and 100° C. are reported for the cited prior artefforts below in Table 16, for which such information is available. InTable 16, “N/R” means “not reported” for that particular reference.

TABLE 16 Cited prior art properties Best dynamic Best dynamic Prior BestMelt viscosity at 40° C. viscosity at 100° C. Art Onset (° C.) (in m ·Pa · s) (in m · Pa · s) Ref. 1 −20 (pour Point) N/R 3 (KinematicViscosity in cSt) Ref. 2 −50 (Melting point) 16.5 3.46 (calculated) Ref.3 −37.7 8.6 N/R Ref. 4 −42 (Pour Point) N/R N/R Ref. 5 −56 N/R N/R Ref.6 −43 679 58.6 Ref. 7 N/R 400.5 43.9

In addition, none of the cited prior art documents provide details ofthe offsets of melt for their respective compounds. The offsets of meltare important because they establish at what temperature the particularcompound is completely free of solid material, and is a much moresensitive measurement because of this than pour point or cloud point.

Several of the compounds described in this invention have superiorlow-temperature fluidity properties, meeting one of the majorrequirements for natural oil derived lubricants. Low temperatureproperties are important for lubricant pumpability, filterability, andfluidity as well as cold cranking and startup. Furthermore, the onsetsof melt demonstrated by the compounds of this invention are as low as−80° C., besting the cited prior art references in this aspect.Therefore, one improved utility of the compounds of this invention isimproved low temperature fluidity or low temperature crystallization.

Table 15 also recites the viscosity at 100° C. of all the compoundsdescribed in this invention. If one compares these viscositymeasurements with those of the cited prior art, it is clear that theviscosities of the compounds described by this invention span a muchlarger range, and many are as high as and higher than the highestviscosities of the cited prior art at 100° C. Furthermore, with therange of viscosities at 100° C. of the compounds described in theinvention which have onsets of melt equivalent to or less than −40° C.,one can see that the range of viscosities at 100° C. which also havesuperior low temperature fluidity is competitive with the highestrecorded viscosities of the cited prior art and offers a much largerviscosity range at this temperature. Furthermore, with the range ofviscosities at 40° C. of the compounds described in this invention whichhave onsets of melt equivalent to or less than −40° C., one can see thatthe viscosities of compounds in this invention which melt at or below−40° C. are vastly superior to the viscosities of the majority of thecompounds of the cited prior art, and such compounds outperform theestolide technology in low temperature fluidity in the cited prior art.

It should also be mentioned that all of the compounds described in thisinvention are Newtonian (characterized by having a shear stress that islinearly proportional to the shear strain rate) from sub-zerotemperatures to 100° C., and that we have been able to developpredictive models which relate the structure of the compounds to theirviscosities.

Therefore, another improved utility of these compounds that is claimedis vastly improved viscosity ranges with enhanced low temperaturefluidity.

Oxidative Stability

Another important area for improvement of natural oil derived lubricantsrelate to their oxidative instability due to the presence ofcarbon-carbon double bonds. It should be noted that all of the branchedcompounds in this invention are completely devoid of double bonds. Theyinherently therefore are significantly improved in terms of oxidativestability compared to natural oil derived compounds with remainingdouble bonds. As commonly understood in the art, oxidative stabilitydefines durability of a lubricant and its ability to maintain functionalproperties during its use. Therefore, another improved utility that isbeing claimed is improved oxidative stability.

Thermal Stability

Another important area for improvement for natural oil derivedlubricants is in their thermal stability. Thermal Gravimetric Analysisfor certain compounds described in this invention (compounds A, B, C, D,E, F, G, A2, C2, E2, G4, H5, H6, H95, H120A, E95, E120, F95, F120, G95,G120 and G140 have been run by TGA) shows that the thermal stability ofthese compounds were surprisingly high, with these compositions havingthermal stability between about 300° C. through about 390° C. Below inTable 17 shows degradation temperatures and associated weight lossvalues of the compounds run by TGA.

TABLE 17 Degradation temperatures and associated weight loss values ofthe compounds run by TGA. T1 Loss3 Sample (° C.) Loss1 (%) T2 (° C.)Loss2 (%) T3 (° C.) (%) A — — 317 81 — — B — — 322 84 — — C — — 350 76 —— D — — 329 85 — — E — — 259 81 — — F — — 260 82 — — G — — 197 81 — — A2— — 327 62 414 99 C2 — — 391 66 G4 — — 324 63 415 99 H5 — — 345 45 42392 H6 — — 343 41 424 93 E95 — — 305 58 — — E120 — — 309 58 — — F95 — —313 54 — — F120 — — 319 56 — — G95 290 46 345 84 415 98 G120 295 10 30656 415 98 G140 289 53 346 89 413 98 H95 221 2 345 39 423 91 H120A — —350 39 443 87 H120B 220 4 342 39 423 90

Hydrolytic Stability

Another important area for improvement for natural oil derivedlubricants is in their hydrolytic stability. In table 18 below, thetested samples exhibit hydrolytic stability for up to 26 hours:

TABLE 18 Hydrolytic Stability Room Temp. 60° C. for 26 h Sample pH¹ pH¹A2 3.8 3.6 H120 3.8 3.6 H120C 3.4 3.2 H120-20H 3.3 3.2 ¹For the pHtests, 3 g of sample were mixed with 7 g DI H₂O in scintillation vials.The pH of the aqueous layer was then measured with a Mettler Toledo pHprobe using a two-point calibration. The room temperature pH sampleswere mixed by briefly shaking the vials in hand, while the 60° C.samples were mixed in a shaker.

The foregoing detailed description and accompanying figures have beenprovided by way of explanation and illustration, and are not intended tolimit the scope of the appended claims. Many variations in the presentembodiments illustrated herein will be apparent to one of ordinary skillin the art, and remain within the scope of the appended claims and theirequivalents.

What is claimed is:
 1. A lubricant base stock composition comprising acomplex ester having the formula (II):

wherein n1=between 0 and 8; wherein n2=between 0 and 8; whereinm1=between 5 and 9; wherein m2=between 5 and 9; wherein k1=k2=5 orgreater; wherein P═OH or OCOR; wherein Q=OH or OCOR; wherein S═OCOR orOH; wherein T=OH or OCOR; wherein U═OH or OCOR; wherein V═OH or OCOR,and in groups P, Q, S, T, U, and V, R=CiHj, wherein i is 2 or greaterand j is 5 or greater.
 2. The lubricant base stock composition of claim1, wherein the composition has a melt onset of between about −61° C.down to about −75° C.
 3. The lubricant base stock composition of claim1, wherein the composition has a crystallization onset of between about−26° C. down to about −52° C.
 4. The lubricant base stock composition ofclaim 1, wherein the composition has a dynamic viscosity at 100° C. ofbetween about 27.5 mPascal Seconds to about 56.1 mPascal seconds.
 5. Thelubricant base stock composition of claim 1, wherein the composition hasa dynamic viscosity at 40° C. of between about 210.3 mPascal Seconds and773.0 mPascal seconds.
 6. The lubricant base stock composition of claim1, wherein the composition is void of carbon-carbon multiple bonds forenhanced oxidative stability.
 7. The lubricant base stock composition ofclaim 1, wherein the composition thermal stability between about 300° C.through about 390° C.
 8. A lubricant composition comprising thelubricant base stock of claim 1 and one or more additives selected fromthe group consisting of detergents, antiwear agents, antioxidants, metaldeactivators, extreme pressure (EP) additives, dispersants, viscosityindex improvers, pour point depressants, corrosion protectors, frictioncoefficient modifiers, colorants, antifoam agents, and demulsifiers. 9.A lubricant composition of claim 8, wherein the lubricant composition isused in an application selected from the group consisting of two-cycleengine oils, hydraulic fluids, drilling fluids, greases, compressoroils, cutting fluids, milling fluids and emulsifiers for metalworkingfluids.
 10. A lubricant base stock composition comprising a base esterhaving the formula (III)

wherein n1=between 0 and 8; wherein n2=between 0 and 8; whereinm1=between 5 and 9; and wherein m2=between 5 and
 9. 11. The lubricantbase stock composition of claim 10, wherein the composition has a meltonset of between about 15° C. down to about −19° C.
 12. The lubricantbase stock composition of claim 10, wherein the composition has adynamic viscosity at 100° C. of between about 1.0 mPascal Seconds andabout 7.5 mPascal Seconds.
 13. The lubricant base stock composition ofclaim 10, wherein the composition has a dynamic viscosity at 40° C. ofbetween about 1.7 mPascal Seconds and about 28.0 mPascal Seconds. 14.The lubricant base stock composition of claim 10, wherein thecomposition has a crystallization onset of between about 26° C. down toabout −20° C.
 15. A lubricant composition comprising the lubricant basestock of claim 10 and one or more additives selected from the groupconsisting of detergents, antiwear agents, antioxidants, metaldeactivators, extreme pressure (EP) additives, dispersants, viscosityindex improvers, pour point depressants, corrosion protectors, frictioncoefficient modifiers, colorants, antifoam agents, and demulsifiers. 16.The lubricant composition of claim 15, wherein the lubricant compositionis used in an application selected from the group consisting oftwo-cycle engine oils, hydraulic fluids, drilling fluids, greases,compressor oils, cutting fluids, milling fluids, and emulsifiers formetalworking.
 17. A lubricant base stock composition comprising a baseester having the formula (IV):

wherein n1=between 0 and 8; wherein n2=between 0 and 8; whereinm1=between 5 and 9; wherein m2=between 5 and 9; and wherein k1=k2=5. 18.The lubricant base stock composition of claim 17, wherein thecomposition has a melt onset of about 22° C.
 19. The lubricant basestock composition of claim 17, wherein the composition has a dynamicviscosity at 100° C. of about 7.1 mPascal Seconds.
 20. The lubricantbase stock composition of claim 17, wherein the composition has adynamic viscosity at 40° C. of about 25.4 mPascal Seconds.
 21. Thelubricant base stock composition of claim 17, wherein the compositionhas a crystallization onset of about 19° C.
 22. A lubricant compositioncomprising the lubricant base stock of claim 17 and one or moreadditives selected from the group consisting of detergents, antiwearagents, antioxidants, metal deactivators, extreme pressure (EP)additives, dispersants, viscosity index improvers, pour pointdepressants, corrosion protectors, friction coefficient modifiers,colorants, antifoam agents, and demulsifiers.
 23. The lubricantcomposition of claim 22, wherein the lubricant composition is used in anapplication selected from the group consisting of two-cycle engine oils,hydraulic fluids, drilling fluids, greases, compressor oils, cuttingfluids, milling fluids, and emulsifiers for metalworking.